Well, if you run some CPU intensive stuff (like a folding client or benchmark) and the computer doesn't lock up, then that will tell you that the CPU isn't overheating.
As long as there is good contact between the CPU, the shim, and the heatsink, it should be ok. I used to do this sort of thing when using laptop P4 CPUs in desktop boards. They required a spacer, so I lapped (sanded very flat) pre-1983 pennies to have a nice copper spacer that is about the same size as a CPU core.
When you say "plenty" of thermal compound, just make sure you don't use too much or it will actually inhibit optimal thermal transfer.