Okay, let's see - first things first. After you give birth and they do all the vitals on the baby, you will have your first breastfeeding session. I don't think I realized this, or forgot about it with all the labor business going on, but it totally caught me off guard. You're beyond exhausted, emotional, and (if you had any drugs) still a little loopy in the head. This is not a great combination for breastfeeding since it is not easy at first (for you or the little one... neither of you knows what you're doing). Be prepared for this.
Second, even if the hospital has lactation consultants, chances are good that you will give birth outside of their "consult" hours. This makes it very important to have a nurse with you during that first session that knows what they're doing. Don't be afraid to ask for help for this first session.
Study up on what good latch looks like now. If the baby has bad latch during these first few sessions, you will end up with lots of nipple damage that will take weeks to heal. I'm not sure if I could have avoided this anyway, since it really is a little trial and error to see what works well for you and baby, but I did not know what good latch even looked like beforehand.
Along with good latch, be patient. If the baby's mouth is not open wide enough or the latch isn't good - take the baby off immediately and try again (break the suction with your finger). This most likely will result in the baby crying/screaming. Breathe, relax, and do it right. I tried to just "tough it out" and keep the baby latched, because the crying seemed so awful. Again, this only resulted in lots of nipple damage that took weeks to heal.
If your baby will take a nipple shield, you may want to use this for the first several sessions until you start to get more comfortable. This could save you lots of unnecessary nipple damage also.
Have the nurses or lactation consultants show you how to execute all the different breastfeeding holds. I almost left the hospital without someone showing me the proper way to do the lying down hold, and this one is a lifesaver for middle of the night feedings!
If you have a lazy eating baby (meaning they will nibble for a few seconds and then fall asleep), have the nurses show you different ways to wake them up. Better yet, you can wake them up beforehand with a diaper change or stripping them out of their jammies (if they're colder, they won't be so quick to fall asleep). I avoided this, because I thought it would be easier to let the baby fall asleep on the breast so that I could maybe get some sleep also. This does not happen - that sleeping baby will just wake up in 20 minutes still hungry.
By the same logic, I was also afraid to burp the baby at first, because he was fast asleep and I wanted to catch some zzzz's also. Again - this won't last. Baby's with upset tummies that need to burp don't stay asleep very long. So, do your best to keep baby awake for the full feeding session and burp afterwards. Some rocking or cuddling should help baby fall asleep later (and with a full satisfied belly, will stay asleep long enough for you to get a nap).
Lastly (well maybe not - I'll probably think of more), if breastfeeding hurts after a week or two (and your nipples are healed up)... talk to your Dr! I mentioned this to the lactation consultants and got blown off as "oh, you're just getting used to breastfeeding... that's normal." Pain - other than initial latch on - is NOT NORMAL. It took 3 weeks before I was in enough pain to cry through each breastfeeding session to finally talk to the dr. and get us both diagnosed with thrush. Miles and I are both on medication and things are only slowly starting to get better. I hope that none of you gets this, but it is more common and more overlooked than I realized. If you get this, let me know. You will most likely have to be your own advocate to get the right diagnosis and medication (I can give you lots of info to help).
Wow - sorry for the novel. There really is a lot to breastfeeding. And whoever said it comes naturally, is lying

But, it is an awesome bonding experience and so rewarding to see baby rack up the pounds after a few weeks of breastfeeding.