For your first two questions.. Yes check pH after adding nutrients. Nutrients will change the pH of your water so if you do it before adding nutes your reading will not be representative of what your plants are actually getting fed. For your second question, this is debateable, and what it ultimately comes down to how much effort you want to put in, and how much you care. Some theories are that the pH of runoff will be way off so it is invalid info, others say it's valid. Personally, I'm not sure, but I check it only if plants are showing a deficiency. A more accurate and accepted form of measuring the pH of the medium is the slurry test.. IF interested do a search on that.
Always check pH of what your feeding.
For ppms..to measure them you need a PPM meter. You should always check this.. both what your feeding and the runoff. Once again it comes down to how much you care... If you do measure PPMS of both what you put in and what comes out, you can get a basis of how your plants are eating. If its coming out with higher ppms than what you're putting in(150+ ppm over whats going in) then that means your feeding too heavily, and may want to cut back a bit. If it's coming out low, it means the plants are eating more than you're giving and you can safely raise your nute levels..
Another piece of advice. If you do decide to be meticulous about measuring these, I would suggest keeping a log of these numbers. If something comes up in 2 weeks where your plants are looking sad, you're able to look at your log and see what's been going on.
my .02