Madrid airport is to the east of the city but Talavera de la Reina is south-west of Madrid, on the E90, so the first part of your journey involves negotiating the Madrid ring road. After that, it's a direct road from Madrid to Talavera.
ViaMichelin quotes the distance from the airport as 141km and estimates the driving time at 1 hour 28 minutes:
http://www.viamichelin.com/
If you wanted to travel by rail, you'd first need to take the underground to Atocha-Rente station. (Line 8, followed by Line 4, changing at Bilbao station, 45 minutes). Then take a direct train from Atocha station to Talavera de la Reina. (About an hour and a half).
Chris