Thanks all for the suggestions. Julia's pix are great and make me glad Orvieto is on my itinerary still.

In the end, I laid them out for my DH 'cause I could not decide (I needed 4 weeks to do the vacation I wanted).

Here's what we settled on:
Arr Milan; train to Bologna
3 days in Bologna (still up in the air)
Train to Orvieto
2 nights at Casa Flavia (http://www.casa-flavia.it/)
Pick up car, drive to Montepulciano via Assisi (I know, not exactly a direct route)
4 nights in Montepulciano (Politian Apartments)
Drive to Milan with afternoon stop at CT
Stay at airport hotel, fly out.

I debated about staying in Pienza. Since we will be in Italy in mid-October, I plan on being back in our base most evenings, so that we are not out driving after sunset. I thought there might be more to do in Montepulciano, but maybe that's a false assumption.

Also, I was spending wayyyy too much time searching out places on the internet as I debated also among Assisi, Spello, Pienza, etc. I am supposed to be putting together a business plan for a small business we're starting--this trip is a last fling.

Again thanks.

great info.