"Hop off-hop on"train travel in Italy

All of your routes require separate tickets. No hop on hop off. You can just buy tickets from a kiosk.
There is a train to Montepulciano from Siena but it does not stop close to the town. It is about 6 miles from the old town.
You would be better to take a bus to Montepuliciano

If you want to hop on off, you must use regional trains and purchase a ticket for each stop.
Regional trains stop at every station, so they take longer, but they're very inexpensive.

Yes, you can connect Siena and Montepulciano.
This too is a regional train which connects Florence and Siena to Chiusi. This train is faster
(1:05)than the bus direct (1:45) from Siena. Bus from Montepulciano Station into town 5 min. Be aware of the times this bus picks up/departs before you buy your train tickets.

Do check return times for both if you plan on a day trip.

https://www.trenitalia.com/en.html

Make sure you hit the regional tab at the top in red. To see where else it stops hit the info button at the bottom...then once again.

Edit: there are left luggage facilities in both the Pisa and Bologna stations.

Do check return times

Scythian, the busses do not connect with each train, but if you continue on to Chiusi, those connect hourly to Montepulciano. (55min)

Will look for timetable Montepulciano Station
Google search will also bring up times and date a month out.

Edit. Could it get tiemme spa/busfox to work but this gives busses.
https://moovitapp.com/itinerary?from=Montepulciano%20Station%20&to=Montepulciano%20&tll=43.318761_11.330795&customerId=4908&metroId=2680&lang=it&ref=5

For something like Venice to Florence, you have seat reservations on the high speed trains, so that precludes hoping off and on. If you want to do a stopover, you might think about taking a Regionale Veloce from Venice to Bologna. It is almost as fast as the high speed trains, but makes a few more stops along the way. It is always the same price, and you can just buy tickets at the station before you go.

Bologna to Florence you really do need to use the high speed trains as they use special tracks that cut through the mountains and get you to Florence in only about 35 minutes.

nancy,

The major cities are covered by the high speed trains and you can not hop on & off those trains. They have compulsory seat reservations which are specific to train, date and departure time, and if you board a train that you don't have reservations for, you'll face hefty fines which will be collected on the spot!

On the routes going to the smaller centres, such as the Cinque Terre, trains are often a mix between Freccia / Intercity / Regionale trains. Intercity trains also have compulsory seat reservations. With Regionale trains, one important point to note is that if you buy tickets locally, these must be validated (time & date stamped) prior to boarding the train on the day of travel. Failure to do so can again result in hefty fines.

Your best bet is to buy tickets for each of your trips. You can save money with advance purchase tickets on the express trains, but not that the cheapest tickets are non-refundable and non-changeable once purchased.

How are you planning to get from Bologna to the Lamborghini factory & museum?

The best way to hit these smaller, remote locations is with a car. How do you even plan to get to the Lamborghini factory from the train station?

Thanks for all the advice. There is a bus, #576, that goes to the Lambraghini Factory. It is a few blocks from the train station, so that is not a problem. So I guess we'll buy two separate tickets from Venice to Bologna and Bologna to Florence. It is all very confusing though. Thanks again.

What is the bit that confuses you, Nancy?

Nancy,

As you plan to take a Bus, the tickets for that may need to be validated also. All of this information isn't really too bad, once you learn the "rules".

Thanks Ken, I appreciate the encouragement. That's the thing, we just never travel by train or bus in the States. I know we'll figure it out and can't wait for our first trip to Europe for our 30th anniversary!!

Wouldn't an Italian rail pass provide the flexibility that nancy's looking for? I know its not the most economical option, but its not always about the money.

A ticket gets you from point A to point B. Interim stops are not allowed. Buy the long distance tickets in advance to save money. Buy the regional tickets whenever, doesn’t matter. It’s pretty simple, really.

"Wouldn't an Italian rail pass provide the flexibility that nancy's looking for? I know its not the most economical option, but its not always about the money."

NO, a rail pass is not the answer and won't provide any more flexibility. As the OP will be using express trains (Freccia, Intercity) for many of the trips, reservations for each train would be required, even when using a rail pass. As I mentioned above, reservations are specific to train, date and departure time, so can't be used for a "hop on / hop off" scenario. I can tell you with absolute certainty that if a rail pass holder is caught on an express train they don't have a reservation for, hefty fines will be charged!

One other point to note is that I don't believe rail passes can be used on Italo Treno.

Using a rail pass only with Regionale trains is certainly an option. However as you noted, this is not the most cost effective option and will be more expensive than using locally purchased Regionale tickets (which are relatively cheap).

I've just booked our important leg for our flight home....Rome to
Venice on the high speed train.

Hopefully not on the same DAY as your flight home?

I think there's some confusion about the different types of trains in Italy so some reading up will be helpful:

https://www.seat61.com/Italy-trains.htm

Roughly, there are trains with reserved seating only, and you must take the exact train at the exact time to the exact destination your ticket is for: no deviations. Then there are slower regionale trains, which have no reserved seats but a 4-hour time limit on the tickets - which must be validated (time-stamped) before boarding. You have to know what sort of ticket you have for what sort of train. Understand as well that not all train stations are going to have luggage storage. This may be true of Carrara and is not unusual among other smaller stations.

In short, the train system is not designed for hop-on, hop-off travel.

Kathy......no, not on the same day as our flight home!!
Thanks everyone for all the information, very helpful.

Whew! I was a lil' bit worried for you there! 🙂