We preferred Lucca and Montalcino in the Tuscan Hill Country. Small walled medieval city states. The bigger blockbuster location, Florence, was a bit much for us. Sienna makes a nice intermediate sized destination with a very nice Duomo (cathedral). We saw lots of sport riding around Voltarra and Castel San Gimignano. Montepulciano was a zoo and we bailed out without stopping.
From Lucca we drove north towards Castelnuovo di Garfagnana, then, just by sight, up to some of the pianos (hillside/mountainside towns above the valley). These proved to be rarely visited and although they were without services we very much enjoyed walking around them and talking to the locals who were delighted to see us. We were in a cage, but I was totally panting for a bike up in this area.
We also enjoyed Milan, in a sort of NYC/Greenwhich Village sort of way. Castello Sforzesco (if nothing else, you must hear an Italian pronounce this name) is the city museum of Milan. In it you may find yourself alone with a completely unassuming Michelangelo piece. We certainly preferred the more intimate, less crowded and less well known venues, such as this one. The castle itself is a bit more modern than much of Italy, if I recall dating to about ad 1500. But the frescoed ceilings are a joy, as are the courtyard windows.
We visited the Cinque Terre, Vernazza in particular. I will give it this: The most beautiful and scenic place I have ever been. The price being that it has gotten a little too popular for it's britches... a lot very unhappy tourists there in our observation. Planned properly it could work out. Walking between the Cinque Terre villages (had the Vernazzians not made it impossible for us to do so, as we had planned) seems like a very nice thing to do. All in all, I would avoid the Cinque Terre unless it seems like something you just couldn't miss.
We did not really like Rome as much as the other areas we visited. However, the Villa Borghese is another of those intimate museum venues, and it is overflowing with blockbuster pieces. I would put up with Rome just for that.
Here is a write up with links to pics I did in another forum.
http://bmwsporttouring.com/ubbthreads/ubbthreads.php?ubb=showflat&Number=419765&Searchpage=1&Main=38791&Words=vernazza&Search=true#Post419765