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Monepulciano to La Spezia. Train or drive?

My adult daughter and I are renting a car in Siena and driving to Montepulciano. Our next destination is Cinque Terre. I can return the car in either Siena or La Spezia. Neither of us has ever driven in Italy. My question is should we,and would enjoy, driving from Montepulciano to La Spezia?
Does anyone have a suggested route? Would prefer scenic to fast and want to avoid cities,especially Florence.

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Return it in La Spezia. There should be no need to backtrack, nor to pay for an additional train ride from Siena, and no fee to drop at a different location within Italy.

The time I did this drive, I went via Massa Maritima (lunch stop) and Volterra (overnight stop), two hill towns I had not previously seen. Heading north on the most direct road between Volterra and Lucca (probably on SR 439) took me through flat farmland, so you might prefer the more westerly Hwy E80 for that section.

On a different trip along the coast, I enjoyed a picnic and swimming stop on the shallow inlet at Populonia/Baratti, and it's also possible to visit Etruscan ruins there. North of that is a long, wooded park with more beach access, and then the town of San Vincenzo, which is pretty easy to navigate and find parking, if you need any supplies or want to stretch your legs near the marina.