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Are you sure you need to stop overnight? It's less than a 5 hour drive, with a good road (a freeway) all the way. I looked on my map and didn't see a town that jumped out at me as an overnight stay.
The Parador Almagro is nice. We're stopped in a few times for lunch while visiting the village, which has the rather unique Corral de Comedias Theatre, but I don't think is quite as interesting as Toledo.