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Rome/Viterbo

Hi

I've posted before seeking advice about itinerary and gotten great suggestions, so I'm back for more. We need to leave Rome, heading for Pitigliano, and pick up a car. We were planning to train to Orvieto to get the car and then drive. But it seems a day trip to Orvieto is in the works for later in the trip, so I'm wondering if there is a different town we can get to be train to pick up car--we'd have a few hours to see wherever that was. Viterbo looks like it is in the right direction. I have 3 questions.

Can you easily do Rome/Viterbo by train?
Is Viterbo worth a look?

If not Viterbo, is there somewhere else that fits the bill (that is, right direction from Rome, reachable by train and somewhere we can rent a car)?