There are other wine regions much closer to Paris than Bordeaux. I think Janet's idea of going to Burgundy (Beaune) when you arrive is good. With one week in France I would spend 2-3 nights in Burgundy (will you be driving while there to see the villages?) and the rest of the time in Paris. Fly to Spain from Paris. San Sebastien and Barcelona are on opposite sides of Spain. You will probably want to fly from one to the other.
When planning a trip I like to think about how many nights I will spend in each place. Two nights = one day, three nights = two days, etc. Don't forget to factor in how much time it takes to get from one place to the next. It will take longer than you think. Getting your things together, checking out, traveling to the train station or airport, waiting for the train/plane, travel time, making your way to your next hotel, then checking in there eats up time. Usually at least a half a day or more, depending on how far you're traveling.
Edit - I just saw your question about driving. If you only have one full day in wine country you could do a tour. With 2 days you might enjoy driving. They have zero tolerance for drunk driving there. If you plan on tasting, go for the tour.