I also drove through London on Saturday and it got my blood pressure rising a little never mind engine temperature. Poor old Tom Tom nearly hit the tarmac for taking me round the S. Circular.
I would be inclined to wait for a nice hot day, let it run up from cold to as hot as it's going to get and give it a few checks.
Start from cold
Does the top rad hose stay cool until up to "normal" running temperature then get very hot?
Does the fan come on after another couple of minutes?
Does the bottom rad hose get rather warm by this point? Should be almost as hot as the top hose.
If you can get to the back of the rad see if it is warm all over (or use an IR heat gun to measure temperature, looking for "cold spots").
If you can't get onto the second stage of the fan try blocking the airflow through the rad to see if it kicks in or short the contacts on the thermal switch to test operation of the relays and motors.
Try the fans with air con both on and off, as the motors are switched differently with air con running.
It's not necessarily a problem to run at 100 deg. c. Some production cars run the coolant at or above 100 as standard these days. It shouldn't boil until 115-120 deg. C with a proper coolant concentration and working header tank cap.
I think possible problems are as follows:
Rad. Fan Thermal switch or relay issue.
Lazy thermostat (not opening fully)
Blocked / silted up radiator
Possibly knackered impeller on the water pump.
Sounds to me like it was basically holding its' own but efficiency is not as good as it should be. However, if it normally runs at 95, it will probably be up to 100 before the fans start, and on a hot day in traffic, it's normal for it to sit at the temperature regulated by the fan switch.
Kevin