Definitely can hire a car in one place and drop off in another. We hired a car in Bologna and dropped it off in Rome.
Italy is a fantastic place to drive, with the Autostrade. It's a bit expensive in terms of tolls, but it is a thoroughly refreshing departure from Ireland, where the motorways last 20 or 30 kilometres at most. In Italy, you can go from Bologna to Florence to Rome to the Amalfi Coast (as we did) on the Autostrade at much faster speeds than comparable distances in Ireland.
Drivers in Italy for the most part are fine. Simply move out of the fast lane when a car is right behind you (usually flashing its lights madly), and it's no problem, at least when you are on the Autostrade. If you are on a two lane road, simply find a place to pull off to let the other cars pass (I had to do this last weekend in Co Mayo to let cars that were right on top of me go by...tailgaters are the same all over the world!)