Unfortunately, there are no public transport options between Toledo and El Escorial. To visit both Toledo and El Escorial in one day, you would need to have a car or take a guided tour:

• Check out a Guided Tour of Toledo, El Escorial and the Valley of the Fallen (Valle de los Caidos)

Toledo to El Escorial by Car

I recommend traveling from Toledo to El Escorial in my Around Madrid Road Trip. However, that assumes you have will start the day in Toledo and end in El Escorial - there is simply too much to do in each to visit all three in a single day.

Only with a guided tour that is familiar with the route and can deal with the practicalities of parking, etc, can you do all three in a single day.
Driving the 100km from Toledo to El Escorial takes around an hour and a quarter, via the A-42 and M-50. Note that the M-50 is one of Madrid's main orbital highways - avoid during busy times!