I see we must go thru Madrid. The train from Segovia to Madrid arrives at Chamartin Station, while the bus arrives at Moncloa Station. And the train from Madrid to Toledo leaves from Atocha Station, which I recall as being huge. I’m nervous about the travel time required from either arrival point to Atocha Station. Is there a preferred arrival point, and how much time should I allow to make a nonfrenetic transfer?
You could use the slow trains from Segovia to Atocha Cercanías, which is adjacent to the high-speed Atocha station.
It saves you from going from Segovia to Segovia Guiomar highspeed station, and it saves you from the Chamartín-Atocha transfer. I don't think you'll lose much more than 45 min going that way, and you'll save money too.