I too have built my own system from scratch...the need for quiet downloading while sleeping was just too great! It doesn't cost THAT much of course once someone else has done all the experimenting for you, unless you are like me and need to play..er, Experiment yourself.
I have not seen anyone stick a heatsink on top of a waterblock before but I do not see where it will hurt. Experiment with the idea maybe adding a fan to that sink that will turn on if the pump fails? I have seen a few reviews where the pump was turned off (in the name of science!) and seeing how long the cpu took to reach an unacceptable temperature. This usually was stated as "It did not work as well as I had hoped, but it gave me more time to shut down my system". There is a program called Motherboard Monitor on the web and it supports a Shutdown program add-in at
http://www.dworld.de called Shutdown Now! You would set the alarm temp to a point above whatever your high temperature in heavy game play and when triggered the system should shut down. I say should because I havent tried to use it yet due to my constant messing...er..tweaking of the system.
I know you said Hardware solution for the shutdown but that is about all that I know of out there for you. by the way, the pvc electrical boxes make great tanks. And a small heater core or transmission radiator is great for getting rid of that heat.
Long winded old cuss ain't I? Haven't typed on this board for weeks and now I need a nap....good luck.