We will have a rental car touring Tuscany from Florence heading south & finishing up in the vicinity of Pienza. We will then head to the Amalfi Coast, specifically Sorrento, via train. Which town is the best for our rental drop off with frequent train travel to Naples? Chiusi or Orvieto? Thank you for your advice.

Why not drive to Sorrento. You can easily drop there and the drive is not bad at all. If you leave early you can even include Pompeii enroute.

I agree with Bob. Why tote all your luggage/stuff onto the train.

I agree too. Drive to Sorrento. It might be a little different if you could get a direct train to Sorrento, but you can't.

snorris,
Both are about the same with Chiusi being a little closer. Chiusi has a Hertz across the street and a Europcar a block and a half from the station.

Henry

Ditto Bob