Hiking and eating in Toscana, any ideas?

Hi all A female colleague is going to have a vacation in Toscana, walking the country from Firenze to Siena (or the other way around :-). She is probably not looking for places like Gavroche to be Spohn-fed with the best food and wine available, but would probably be grateful for discovering hidden jewels on the way. Any of us having any ideas? Thx in advance Anders