There is a good chance that it will hurt while you're getting your attachment sorted and if you get a grazed nipple it is eye-watering, toe clenching agony.
When my milk came in my boobs were like a pair of rock hard, swollen grapefruits - ouch!

That thing where the midwife grabs your boob in one hand and the babies head with the other and attaches them - don't let them do it. It's fast and easy for them but it doesn't help you learn how to attach correctly yourself. Make them teach you with verbal directions and get your DH to watch so that he can help you out with the same directions at home if needed. Try to make sure you're confident with attachment before you go home.

Panadol is a pretty effective painkiller so if things get painful you can use it but it's only a temporary measure.