Hill Town Questions

Siena in one day: yes in my opinion, unless you need to see every museum and church

Montalcino-Pienza-Montelpulciano as a day drive is great. You won't get to see everything, but you will have some fine views, good food, shopping opportunities, and see some culturally significant sites. Again, depends on the level of detail you want in each town. Rick's guide is good at giving an overview and self-guided walks.

I think your overall plan is fine. Volterra and San Gimignano are half-to-full day places IMO. Volterra has a great vibe. Cività is a good lunch stop surrounded by good walking and fabulous views. Don;t go there on a rainy day. Great to see on your way to Orvieto if the weather cooperates.

You can indeed do Siena in a day. Here's an example: find a place to park on outskirts area of historic section. (Check around piazza Gramasci - bus drop off area.). Walk to Il Campo. Enjoy the the Square for a few minutes. Go to city hall/tower on the square. Climb to top of tower and enjoy great views and take photos. Climb tower as soon as it opens around 10 am. Hard to get down steps once place gets busy. See the famous painting of good/bad government if desired. Right next to City Hall is a street with a name like Giovanni. Walk downhill behind city hall. Take a left down a ramp. You will see a flea market. Next to market, on right hand side, is a trattoria. Trattoria Papei. We ate here twice for lunch. Moderate prices compared to elsewhere. Good food and service. The melon and prosciutto appetizer was excellent. I'm not a big melon fan; but Siena's cantaloupes are sweet and delicious compared to my home. Won me over. After lunch, go to Duomo complex and enjoy the stunning Cathedral and its museum, baptistery. Seeing San Domenico is only a must-see for those who want to connect with St. Catherine of Siena or who have more time.

If anyone has any suggestions on off the beaten track Val d'Orcia roads/smaller towns to explore, that would also be helpful.

LJ

I think your timing is fine and allows a comfortable flexibility. The Michelin map specific to Italy Central has a good level of driving detail and marks the more scenic roads in green.

In the pienza area stop by a farm for some cheese making and lunch at the place. I loved http://www.podereilcasale.it/farm this past year. Amazing lunch and tour.

1. Siena in one day: YES
2. Montalcino, Pienza and Montepulciano in one day: YES
3. SG, Pitigliano, Civita and end in Orvieto. YES DOABLE.

For Lucca I suggest to devote all day to it (plus maybe an hour in Pisa). Lucca is farther away, so you need to take the travel time into account. Avoid going there on a weekend as you will encounter the traffic caused by the Florentines heading to the beaches (although in October it might be too late for beach weather).

You can easily pair Volterra with the San Gimignano visit. They are close to each other and you don't need all day for either one. San Gimignano can be seen comfortably in a couple of hours, including taking the pictures.

We considered renting a car while in Siena because we wanted to visit Montepulciano but as we have researched it sounds like it's necessary to get an Italian license of some sort. Have you found that to be true? We have also been a bit scared off by the talk that tickets are extremely high and tourist are targeted. Originally I had heard that driving in the area was fairly easy but now I'm not certain. Just wondering if you had seen or found any of this to be the case.

I see this question tagged on Linda's topic - there's a bus that goes to Pienza & Montepulciano from Siena, so a car isn't necessary.

Good to know. Thank you and have a great trip Linda.

kbug96:
Driving in Tuscany is easy and it does not require any special Italian drivers' license (just an International Drivers' Permit, which is issued in 10 min. by your local AAA).
Fines are not higher than they are elsewhere, and I doubt the automatic cameras can detect which speeding cars are driven by tourists as opposed by locals.