After leaving Rome (this September), my daughter (25) and I want to explore Tuscany mostly the countryside. As much as I want to see Florence, I don't think I can handle several more days in a big city after being in Rome. I am a nature lover. What is the best base for us to explore from , maybe some place to rent an air bb for 5 days and take day trips to some off the beaten path places. I would love to see Assisi also but I don't know if that's possible in the context of this trip. We need to make it down to Naples after this to either spend a few days on Amalfi Coast, or if we decide to skip that, she at least wants to see Pompeii (I saw it as a child) and we are flying out of Naples home. It is a 2 week trip. I am not totally against a car rental, I just don't want to have a car in a big city or on major highways
We are very fond of Orvieto which is a short train ride from Rome. I can highly recommend Casa Selita B&B (https://www.casaselita.com/en/) which is a very short walk, but uphill, to the elevated town.
I really like Orvieto- I've stayed there 4 times for several days at a time. I've rented a car there and visited Assisi (stayed there for 3 days to visit towns in the area). You need a car to see places off the beaten path. There are plenty of small towns to stumble upon as you are driving. I've been to many and there are still so many to see. I do not recommend driving in Naples (we've done that). This past year we rented a car in Salerno to explore the area. Much easier to drive from Salerno. Paestum is worth a visit if you are near Salerno.
Your best bet to see Assisi is from Rome’s Termini train station. There is a 2h 15m direct train departing at 8:02 AM and you can depart for Rome at 6:38 PM.
Since you want to explore Tuscany (Orvieto is in the region of Umbria) I recommend staying in Siena which is a 1h 15m direct bus ride from Florence and sleep in the old town. Good day trip options by public transportation are:
Direct train from Siena to Montepulciano (1h 15m) but you’ll need to take a taxi from the train station to the city center. I would also make sure I had the names of taxi companies along with their phone numbers when arriving in Montepulciano if none are outside.
Another good day trip from Siena is a direct bus to Sam Gimignano (1h 15m).
You could take a short train ride from Rome to Chiusi and rent a car. From there it's an easy ride to either Radda in Chianti or Pienza, which are both great little towns to use as a base for exploring the Chianti area and the Val d'Orcia area, respectively. Chianti and Val d'Orcia have many old "off the beaten path" Medieval villages and castles, but you will need a car to get to most of these kinds of places. Please see the private msg that I sent you for more info.