Sal, may I suggest a visit to the Perigord and the Gers area. If you're looking for historic places, good food, pleasant wines you'll have a hard time finding a better area! Look up a map of France and search for the Auch and Périgueux cities. Sarlat in the Périgord is a must see small city. Sarlat
The area should be avoided during the touristy Summer season.
Roads are no problems there.
As for driving from Barcelona into France, I presume you will have a rental car with Spanish plates which means you will cross the border without noticing you have changed countries. This is one of the glories of the EU. No more controls at customs!
If you need more specifics, just ask!