Sounds like a great trip! Here are my suggestions:
go directly to Sevilla on the AVE train (you'll be jet-lagged, so no sense seeing Madrid for one day only), and settle in to Sevilla for 3-4 nights. Try the Hotel Simon--we loved it. Then rent the car to tour the white villages. Pass through and see Arcos de la Frontera and continue on to Grazalema--it's adorable. Stay at Casa de las Peidras tel/fax (956) 132014 and definitely eat there--they have some of the best food in Spain. Then continue on to some of your other destinations. You might want more than one night for Granada. Another white village which is wonderful is Cazorla, in Jaen province.
You might think about renting the car in Sevilla and returning it in Madrid. It won't cost you any more, and it would free you up to see places like Cuenca (truly amazing), the windmills of La Mancha fame, and lots of other interesting, non-touristy places. In Toledo, try the Almazara, a manor house with fabulous views of the city. If you do a search on this board for any of these places, and many others, you'll get lots of information. I wonder if you could fit the Costa de la Luz (on the Atlantic between Cadiz and Tarifa) in to this trip. Might be a perfect time of year to see that. Whatever you decide, you will love it--you'll wish you could see/do more, and stay longer but you'll enjoy it all. Have a wonderful time.