There is an Enterprise car place between Bletchley Park and Bletchley station, about 2 or 3 minutes walk from either.
I don't know about any other major brands at either Bletchley or Milton Keynes.
Both Milton Keynes and Bletchley are good stations for getting into London as long as it isn't at rush hour going in. Tickets do however cost more during the evening rush hour - from 4 to 7 inclusive pm, slightly different times between the Virgin and London Northwestern trains - and there are frequent trains on both companies from Milton Keynes Central. Virgin have the fancier trains and run non-stop from Milton Keynes Central to London Euston. Slightly smaller doors and a bit more of a step up but easy. xx:00 (some hours), xx:03, xx:47 and sometimes others. The front third of their trains are First Class, probably not worth it for such a short journey).
London Northwestern run the commuter trains from Milton Keynes Central and their xx:07 (stops only at Watford Junction and Euston), xx:15 (nonstop), xx:22 (slow, stops Bletchley and 4 more times before Euston), and xx:41 (stops only at Bletchley and Leighton Buzzard before London Euston) all have double sliding doors and are virtually all standard class (First class only has 24 seats in a small compartment in coach "B" of each of these trains. Not worth it for such a short journey.
There are more staff about at Milton Keynes Central who can answer questions, but it is always a very busy station.
There may be one person in the booking office at Bletchley (or not) and there may be somebody on the barriers there (or not). The lifts are more reliable at Milton Keynes Central and they are larger and more modern, but the grotty ones at Bletchley work most of the time and will get you up to the overbridge and down to the platform usually. The stairs at both stations are fairly steep - because it is an overhead electric line you have to go up the equivalent of 2 storeys to cross over.
There are 3 trains most hours to London. The xx:27 is slow and stops 4 times. The xx:46 is fast and only stops at Leighton Buzzard 7 minutes later, and is then express to London, and would be my choice. The third possibility is the xx:52 is very slow, stopping 6 times on the journey.
It is a shame that you will have all of the party and all of the luggage when you get to London. I can't think of a better way to do it at the moment, but shepherding your mother in law and the luggage onto the train and off again may take forethought. Perhaps you could drop everybody and luggage at the station then return the car - and hope for a dry warm day.