On our flight back from Africa, my friend and I had a 7-hour layover in Paris from 6:15am to 1:30pm. We found that that is PLENTY of time to hit the main spots in Paris.
We had a friend of a friend pick us up at the airport and drive us around, but the same places could be hit up in a cab.
In the morning, we did hit traffic getting into Paris, it was about a 30 minute drive into the city, but once there, it was fairly easy to get around.
We first went down the Champs-Elysees and drove around the roundabout that circles the Arc de Triomphe. Then we headed over to the Eiffel Tower where we got out and walked around at 2 different spots. Our last stop was Notre Dame Cathedral where we took a personally guided tour of the cathedral. We then headed back to the airport early to get through customs and find our flight. After seeing all of that and our driving time, we still made it to our gate with an hour or more to spare. I will say though, we asked some of the customs workers how long we should leave to get back through security to get back into the airport and they told us about 30 minutes. Luckily we got done early and came back to the airport early instead of trying to find more things to do, because we ended up being in security and everything else getting to our gate for almost 1.5 hours, 3 times the amount they had suggested to us.
Quick Tips:
Make sure you leave plenty of time to get back into the airport if you're going to try and sightsee on a layover.
If you have time and can get out of your car, I would highly recommend touring Notre Dame. It's more incredible on the inside than anything on the outside.
The best view of the Eiffel Tower is on the hillside at the back of the tower at the Musee de L'Homme (or Museum of Man). This is an especially good view if you don't have time or don't want to take the tour of the tower.
Drive down random streets if you have the chance, there are many little incredible things we saw by just getting lost on the little one-way side streets.
Best Way To Get Around:
I would suggest taking a cab or finding a guide for Paris. Although we did not take the metro, I heard that they were pretty realiable, but slow and confusing. If you're looking for a guide there are travel sites like couchsurfing.com with people who are willing to give tours of their cities. Look them up. The people who live there will know the ins and outs of the city.