selcano,
Nigel provided an excellent summary of the "hop on, hop off" options. For a visit to Orvieto on the way to Siena, I'd suggest buying two separate tickets. If using Regionale trains, the tickets are relatively cheap so no reason to use a HO/HO method. Also, as you only have six hours on the ticket from the time of validation, that will limit the amount of time you'd be able to spend in Orvieto. Much better to just buy two tickets.
One important point to mention - you MUST validate your tickets on Regionale trains prior to boarding the train on the day of travel, or you'll risk hefty fines which will be collected on the spot. The same applies to Buses, Metro, etc. in Italy. if using the "fast" trains such as the Freccia high speed or InterCity, you can only use the ONE train specified on your ticket as these trains have compulsory seat reservations. If you board the wrong train, you'll be deemed to be travelling without a valid ticket and again, fines on the spot!
I'd suggest travel by train rather than bus from Orvieto to Siena (IMO). There's usually one change at Chiusi-Chianciano Terme but that's an easy one. When you arrive in Siena, you'll have to take a Taxi or Bus up the hill to the town, as the rail station is located at the bottom of the hill. I try to avoid renting cars when there are good public transportation options. There are some potentially expensive caveats to be aware of with rental cars in Italy as well.
Orvieto is indeed a lovely Umbrian hill town, and would be worth at least one night. Be sure to have a look at the incredible Signorelli frescoes on the ceiling of the Duomo, and also St. Patrick's Well if you have time (an incredible engineering feat in its time).