First off, the information on this board has been fantastic! I have been feeling very overwhelmed in trying to plan our first trip to Italy on our own but the suggestions have been great.
Our plan thus far is as follows:
Fly into Rome and take the train to Florence
Stay in Florence at the Hotel Caravaggio for 2 days
Rent a car and stay at the Hotel Pescille (outside San Gimignano) for 2 nights - day trips
Leave and stay at the Residenza d'Arte - 2 nights - day trips to Montelpuciano, etc
Drive to Orivieto and possibly stay one night here or drop the rental car off and head back to Rome via the train.
Rome for 4 days (we are meeting a tour so have no choice)
ANy feedback would be appreciated.

1st timer,
Sounds like a good plan. Appears you already have your hotels. The only advice I might have given, was to stay in Siena for 4 days and do your day trips from there instead of splitting it into 2&2. I like that because when you come back at night from your day trips, you're in a larger town to have your passiagiata and dinner.When are you going ?

IMHO yo are planning on staying in far to many places. Each time you change location you use up quite a good deal of holiday time. Even if the drive is just a couple of hours, you nee time to pack up, time to check out, time to load the car, time to drive, time to check in, time to unpack... Basically a two hours drive transfer can take up to 5-6 hours. Infact it uses up a lot more time than driving to a daytrip destination. IMHO, you would use your time better if you picked one single destination in an area of Tuscany other than Florence (Florence is Tuscany too, actually it's the main city of Tuscany and regional capital) and stayed there for 4 full days. Spend the other 3 days in Florence. So, my own plan would be: train to Flroence, stay in Florence for three nights, rent car, stay in Central Tuscany, dayrtip from there to nearby places. On the last day, pack up in the morning, drive south heading to Rome, and visit somewhere in the middle (that could be the day to see Montepulciano), as you arrive into Rome, drop the car (as long as you pick a location that's close to the GRA, the highway ring that surrounds Rome, you don't have to bother with driving in Rome: you will basically staying on the highway all the time, with maybe two minutes of driving in the city itself).