Train from Toledo to Segovia

No direct train, you will have to go into Madrid and change there. Use bahn.de to see the schedules--- much easier than trying to figure out Renfe. There are few options, but a good one has you leave Toledo at 9:35 for the 30-min. Ride to Madrid ( Puerta de Atocha station). Then you have an hour before the train to Segovia leaves from the Cercanias side of the Atocha station. Two more hours and you get in at 13:07.

There is a late afternoon pair that works too.

https://reiseauskunft.bahn.de/bin/query.exe/dn?ld=150100&protocol=https:&seqnr=1&ident=ah.031203100.1468895109&rt=1&rememberSortType=minDeparture&HWAI=JS!ajax=yes!js=yes!&REQ0HafasScrollDir=2

Thanks! I have a bahn.de account and Renfe has been driving me nuts. Suggest buying ticket(s) thru bahn.de also?
Next leg would be Segovia to either Avila or Salamanca on a Sunday...your counsel?

The best option is to take a train from Toledo to Madrid (Atocha station), then traveling to the Chamartin station in Madrid, via Metro or Cercanias (commuter train).

There are several Cercanias (trains) traveling this route as you can see on their website (below)

• You may check Cercanias schedules here:http://www.renfe.com/EN/viajeros/cercanias/madrid/
• Departure Point: Atocha
  
• Destination: Chamartin
• Schematic map of Cercanias routes:http://www.renfe.com/viajeros/cercanias/planos/madrid.html

There are several trains traveling from Chamartin station to Segovia & travel time is about half an hour.
You may check train schedules here: http://www.renfe.com/EN/viajeros/index.html

I've not had any problems checking train schedules or booking tickets on the Renfe website, however,
you may do the same on the captaintrain website: https://www.captaintrain.com/en

You may find this article very helpful, if you want to book your tickets via Renfe
If you book your tickets via Renfe, it's easier to pay with PayPal.

Have a wonderful trip!

If you are interested in an opinion on Salamanca vs. Avila, I'd vote for Salamanca for sure. (Though I liked Toledo and Segovia even more.) I agree with Rick that Avila is just a quick-stop sort of place.

....Suggest buying ticket(s) thru bahn.de also?.......

You cannot. You can only purchase tickets through dBahn that end or start in Germany. However the bahn.de site is great for overall information on schedules.

You can buy the tickets when you are there. There is no price advantage for pre-purchased tickets on these routes. The Toledo trains can sometimes sell out during busy times or the early/late trains. And ticket lines at Atocha can be pretty long. But the Toledo station is small and easy to get tickets at. I'd buy your return ticket when you get to Toledo, before heading up the hill into town. Just have the trains you want written down so you don't forget and to make it easy to buy your tickets.