In one of Rick's videos he looked at a few great small towns in Itally.
He suggests visiting the area around Volterra, south-west of Florence—one of his favorite towns in Italy. You'll find there a great museum of Etruscan artefacts and jewellery. And wild boar is a speciality in this area! There are also many alabaster carvers and a museum featuring alabaster carvings.
A great place to stay when outside the big cities of Italy are agrotourismos—working farms that hire out rooms for travellers, akin to B&Bs.
Another beautiful and interesting city to visit is Chiusure, which holds an artichoke festival each year.
Pienza ia another beautiful small town worth visiting.
Montepulciano, noted for its wines, is a great area to visit for the wine enthusiast.