My recommended option - Taxi
I recommend taking a one hour taxi ride that costs 100 euros, from Madrid airport to Toledo which is about 90 km away.
Yes, a taxi sounds expensive, but consider this. If you are 4 or even 6 people, it makes a lot more sense and it is also the fastest way to Toledo from Madrid airport.
Option 2 - Bus
ALSA runs direct buses from Madrid airport T4 to Toledo. The ride is 90 minutes long and costs only 6 euros one way. But the frequency is not great, with the only bus leaving at 1230pm, arriving in Toledo by 2pm. This is a great option if your arriving flight schedule makes sense. But if your flight lands after this you have no bus until the next day.
Option 3 - via Madrid
Your other option is to take a taxi or train from Madrid airport into Madrid city and then take the train to Toledo. This will not be much cheaper when you add the costs and it will end up taking you a lot longer.
Of course, ideally you can rent a car and drive up to Toledo.