The two main car rental firms at Ancona airport are Hertz and Avis. Don't go for a sporty low hung car - it will just bottom out on the white roads! If you book a Hertz car through the Ryanair website you will normally get a very good deal. It's a good idea to get all the insurances - as if you have to make a claim, the excesses are, well, excessive! The team on the Hertz desk are friendly, helpful and speak excellent English.
Rental cars in Italy normally use diesel (called gasolio) and less often unleaded (called senza piombo or benzina verde). Tell the attendant "il pieno, per favore" (fill it, please). Click for excellent information relating to toll roads and how to use the toll booths.