anything you need to test... like after you mix your nutrients. This will tell you if you should ph-balance it before using it. Runoff is another potential reading of worth, but it's not going to be as precise. before reacting to runoff readings... figure out what those readings look like when you have near-flawless grow cycles... that runoff isn't necessarily representative of what is in the medium after an irrigation... it'll correlate at best and numerous factors will impact just how strongly it does...
hopefully, you get to a point where you rarely need it. I'd suggest the cheap 100-pack of .5-resolution test strips with a 4-color code. last one i bought probably has 60-70 remaining.. and probably won't ever be used, lol. between callibration fluid and proper storage of fluid and equipment, it's probably cheaper and more convenient to use strips, because you don't need .1-ph accuracy.