We spent 3 nights in Montepulciano last September........I'm soooo envious of you! Montepulciano was my favorite hill town!!!
We drove from Florence through the countryside to Montepulciano, stopping in neighboring hill towns, then onto Assisi. Driving was incredibly easy, expedient and oh-so-beautiful! One plan that helped us (Thank you Roberto di Firenze!), is that we rented our car from a Hertz Rental Office in the Oltrarno district of Florence. (The "other" side of the river......One of my favorite areas in Florence.) By doing so, we avoided all ZTL zones and crazy traffic in Florence. (Took a cab from our apt. to the Hertz office.)
We flew home from Rome. So the day before departure, we drove from Assisi to Termi, stopping in Spoleto for a walk and lunch. The Termi train station is just 2 blocks from a Hertz Rental Office. So we dropped off the car, purchased tickets to the Termini in Rome, and took the train to Rome. By doing so, we once again avoided the chaos of driving in a large city. The next morning, we took a cab to the airport. It couldn't have been easier!
Hope you make beautiful memories in Montepulciano! :)