I had a difficult time with this too, now, however, I have no problem whatsoever saying no.
Matter of fact, once I learned how I think I might have gone overboard the other way, but now that has all evened out too.
The next time you have a pressing engagement, simply say, I'm sorry, but I've got an appointment to get to and won't be able to help you out this time.
If they get miffed or upset, that's their issue, not yours.
Trust me, the more you do it the easier it gets and the better you'll feel.
ps. It always calms my nerves a little bit if I inhale deeply yet discreetly before replying.