From Milan, take the A7 Autostrada toward Turin. Near Tortona, exit onto the A21 Autostrada toward Asti Est. Exit A21 at Asti Est and follow the signs to Alba. 146km.
From the Turin Sud entrance to the A6 Autostrada, take A6 in the direction of Asti. Exit onto the A33 Autostrada. Exit A33 at Cherasco onto SP 12. From SP12, make a left onto SP 3 in the direction of Barolo. Continue on SP3. 71km.
From Alba, follow the signs on SP3 south to Barolo. It is 15 km from Alba to Barolo.
There is a free car park on the left as you enter the town. You can park there and get to any of the sights in Barolo in a few minutes on foot. The streets are quite narrow, so parking in the car park is a good idea.
Barolo is easily walkable, although some of the streets are quite steep. You can walk the entire town in 30 minutes.
Barolo is a world famous wine city. It is the namesake city for the "king of wines and the wine of kings." Barolo is a very scenic small town. The surrounding countryside is spectacular. There are some very panoramic views from the Castello Falletti. However, if you are not interested in wine, there is not much to see or do in Barolo. For the non-wine lover, it is probably not worth the drive up from Alba.
A number of the most famous Barolo cru's (specific vineyards) are located just outside the town of Barolo. For example, the cru Cannubi is on the south facing hillside on your right just before you enter the town on the road from Alba.
Taste wine. Taste more wine. Buy wine. There are several good wine shops in town, and a number of famous producers have tasting rooms in the town. Many of the wine shops in town stock aged Barolos from as far back as the 1980s. The owners of wine shops typically have bottles open for tasting, and may open a specific bottle for tasting on request.
One prominent producer with a tasting room in the town is Marchesi di Barolo [Via Alba, 12 - 12060 Barolo (Cn), Tel. 0173/564400 - Fax: 0173/564444].
There in an enoteca in the basement of the Castello Falletti, the Enoteca Regionale del Barolo (closed Thursdays). You can't miss the Castello Falletti - it's the castle at the top of the hill in town and it appears in almost every picture of the town. This enoteca has a lot of local wines from recent vintages and charges € 5 for tasting three wines and € 2 for one wine. The opening hours can be irregular, so you should check in advance before going there to taste (Piazza Falletti, Telephone: 0173.56277 Fax: 0173.560512). There are a number of other good wine shops in town. The other shopping in Barolo is limited. This is not a shopping town, it's a wine town.
By all means. There are a couple of small bars in town, but wine is the main attraction.
Visit nearby wine towns:
Do some hiking in the surrounding countryside. 
There is a web page (in English) for the community. There are a lot of great links to wine producers, hotels and restaurants on this page.