Trains (and Toledo city buses) may be on a Sunday schedule - a little less frequent than weekdays. I would take a train from Atocha and, in Toledo, ask a
taxista to take you on a
panoramica a tour to the heights across the
rio Tagus for some great photo opps. You might even want to have lunch at the
Parador . You can walk around the main part of Toledo at your leisure: San Tomé where you can see El Greco's Burial of the Count of Orgaz, the Synagogue and lots of shops. Have some Mazapan! The overpriced shops at the Toledo swordmakers will sell you damascene jewelry for about half again as much as you can buy it in Madrid. My vote: Do it on your own!