Bleucheese,
Good so you are experienced with the area around siena. I spend a a week in the montepulciano/siena area every year. Here is some of things I've found to be fun. In Siena, just about twenty minutes on the outskirts is castel monastero: I stay here since it's a sweet secluded resort. However, you don't have to stay here but the restaurants at this resort are really, really good. The formal one is a gordon ramsey branded restaurant called contrada but the real deal is the more casual restaurant in the cave (cantina). This is a great place for a romantic dinner. Lots of local italians show up here.
Montepulciano is a great little town. Steep uphills but really cute. Check out
http://www.palazzoricci.com/. This is a music school which does summer performances of classical music. Great for chilling out to performances. Great little restauarant in montepulciano is: Locanda Cicolina just on the outskirts of town. Great food.
Another town to visit is Castiglione del Lago on lake trasimeno. Lake trasimeno is a cool little lake that is refreshing especially if it is warm. There is a nice paved pathway that goes out of the base of the castle here which you can wander.
If you are into thermal spas a famous area is chianciano Terme. I am not a spa person so can't vouch for it although this area is supposed to be nice.
Finally another hidden gem of a restaurant is Il Bucchero in Chiusi. Chiusi is a non descript town but I love this restuarant and make the drive from montepulciano every year to eat here. The owner and chef was a regional champion cyclist so a little bit more appeal. His pizza's are famous and his linguini is fantastic! This place is filled with the locals so you know it is legit.
If you spend three days at riomaggore you can easily see the other 4 towns. You'll know what I'm saying when you get there. Also if you feel a little too claustrophobic in the 5 terre, hit either porto venere or levanto for more action. It's such a short boat or train ride.
Finally, I know you will hate this but something for the wife. There is an outlet mall somewhat near you. This place has some good to great deals. I think the prada outlet is definitely overrated as is gucci. But if your wife knows Lanvin...there are killer deals here. The moncler outlet is not that good. The brioni is decent though if you are looking for a suit for yourself. The gucci cafe is surprisingly quite good.
The Mall
Website Directions 4.01,053 Google reviews[/url]
Outlet mall in Leccio, Italy
Address: Via Europa, 8, 50066 Leccio Reggello FI, Italy
Enjoy your trip and feel free to message me if you have any questions.