Hmmm...Never really thought of that one. I usually test mine before a feeding in the middle of the photoperiod. Not sure really why I do it then other than I don't want the food to alter anything...
Knowing the highs and lows is good idea. As far as when to test, doesn't really matter. The only thing I would suggest is trying to test at the same approximate time each day. This will let you know how stable the tank is which is as important as the actual results of each test.
Macronut, I agree with you. While knowing every little swing of pH in your tank will do nothing but drive you nuts---taking a two week period every now and then to test several times a day can help keep an eye on what your pH range runs and possibly help with diagnostics if need be.