I live in Caterham and really like it. We moved out from South London, Clapham area originally but have been here. or nearby, since having kids, now secondary age.
My secondary age kids go to one of the Croydon independents mentioned by a PP and the primary aged one goes to a private prep so I only really have experience of the private schools. However, I have lots of friends whose kids go to state secondary schools like De Stafford, Warlingham etc and all seem pretty happy with them, kids all seem to get on well. I dont know much about the state primary schools but there are three or four in Caterham. Reigate College is very popular for state sixth form in nearby Reigate and has a great reputation.
We both work from home mainly with a day or two in London but used to commute into London full time. I really like Caterham for that reason. It's very green and leafy with lots of parks and green spaces and very near some lovely countryside, but you can be in London Bridge or Victoria in little more than half an hour. Driving to Beckenham/Kent is very doable from here and there is a good back route you can take in the morning to avoid traffic.
My family live in Wokingham not far from Maidenhead and of course you're right on top of the M25 junction 8 at Caterham which makes it really easy to get there, or down to the coast, Bluewater, wherever. Of course this is theoretical and dependant on the M25 which can be a pig! I can normally get to Wokingham in about 50 minutes but I'd say it would be l hour 20/30 in rush hour.
Caterham town centre is a bit bland/old fashioned but there is a lot of talk and effort to try and improve it. It's perfectly fine for day to day stuff though with hairdressers, barbers, Pizza Express, Waitrose, Morrisons, couple of restaurants and nice Costa/Neros. Reigate and Oxted high streets 15/20 mins away and a bit more vibrant. Caterham on the Hill high street is also improving with some nice delis, cafes and a nice pub.
Could work well for "in the middle between Kent and Maidenhead" - though I think your husband will have the longer journey :)