In option 1 are you walking from San Martin Bridge to Zocodover and in option 2 are you walking from Zocodover to San Martin Bridge and catching taxi from there to the trsin station?
Trying to catch a cab at Saint Martin is probably more difficult. The train station and Zocodover are easier places to get a cab. It would be easier to find another couple on the train to split the cab ride at the beginning of the day rather than at the end of the day.
Arriving at 9:51am or 10:51am gives you approximately 1 to 2 hours before your first timed attraction. The cab ride up to the Mirador and down to San Martin would be a nice and simple filler first thing in the morning and still leave you some time to explore on your way to your first timed attraction. You will also have more energy in the morning to make the walk from San Martin to your first attraction. On the other hand, at the end of the day, you may find that the changes in elevation in Toledo have really worn out your legs. If it were me, I might be inclined to ask the the cab driver to wait at San Martin while I take a few photos before continuing on with the cab ride up to Zocodover. You should find out what is included in your walking tour and you could choose a walking route from San Martin to the first attraction which does not duplicate the later walking tour. Then after you complete your walking tour, you would not be under any pressure to visit the San Martin or Mirador at the end of a long day. You can relax a bit in Toledo, may be even have dinner, which we did, before catching a bus back down to the train station to return to Madrid.