I definitely concur with getting a good guidebook of the Pyrenees. There are also some guides that have driving routes and lots of information about towns and sites along the routes. I think they focus more on the Spanish side but would still be useful for your planning. They aren't the Michelin ones but I forget the name.
I can recommend starting by going north from Barcelona (E-15) to Girona and perhaps staying there a night. You could also swing up to Figueres if you are interested in the Dali Museum, which is pretty wild even if your not an art fan.
The route into the mountains that takes you past Besalu is a good one (from Besalu on it is very scenic). Besalu is worth a stop or even an overnight if you don't stay in Girona. Very charming Medieval town. From there are a lot of scenic vistas and towns perched on mountainsides. The guidebooks will point them out and help you pick the route that most interests you. I've only been as far as Ripoli but the roads to there were good if pretty twisty.