When they were baby-baby eating constantly, it was sooo hard. But I had to do it so that a couple times a day I could give them a bottle and give them food coma so they'd actually fall asleep quickly and stay asleep. So to answer your question of when I pumped, I just missed out on my own sleep in order to pump.
I would also do the leave it out cus I'm gonna pump again in an hour or two thing.
Now that they're a few months old they are more efficient at BFing and can last longer between feedings -- thank god! I was seriously at my wit's end for the first 3 months. I hit the wall and got a little crazed more than a few times. I took it out on my poor hubs, snapping and yelling at him.
So now I pump once a day, usually sometime in the middle of the night or wee hours of the morning when my boobs are getting really full, and freeze it.
Initially I had been planning on going back to work so I was very concerned about the freezer stash, but plans have since changed and I am SAHM'ing, but I still want a good stash in the freezer for my DH and parents to use if I have to go out (like to the monthly mothers of multiples meeting!).