A few things to note:
- Never set anything to set at boot until you are 100% sure it is stable.
- Test one speed at a time.
- Nandroid backups can't hurt.
Onto my testing methods, which aren't too different from orion2001's.
Starting with stock voltages, I go into SetCPU and set the min and max to the same speed (locking it into that speed). I then perform a benchmark for each speed. Antutu or CFBench will work, but they will take a while if you are testing the lower speeds. You may want to run the benches a few times to see what you will be looking at (scores fluctuate a bit between tests). I do this to get a control and so I know what each speed should look like. I write these scores down for each speed.
I then start undervolting on slot at a time. I like to start with the lowest slot, as it is where my phone spends the majority of it's time. I change by 25mV at a time. Using SetCPU I then lock my processor into that speed. I then run the benchmark a few times. I compare scores, making sure they are in a similar ballpark. I do that for every slot.
After I am satisfied with my voltages, I then use my phone as normal (not set on boot still). I look for odd things to happen. Slowdowns, random reboots, problems with apps, inexplicable battery drain, phone getting hotter than normal, are all potential problems of undervolting that may not crop up during tests.