My youngest had a bad latch on the one side, so I started pumping when he was 4 days old and I pumped only for 3 days to relieve myself. With doing that, I was able to start a little stash and I now get around 5-6oz each time I pump (total).
Since going back to BFing as well as pumping, I nurse first thing in the morning (around 6:30-7), then I pump around 8:30-9am. He gets a bottle of my milk around 9:30a. From there, he eats every 3.5-4 hours, and I pump when he eats. If I nurse him at feeding time, I pump around 1-2 hrs afterwards.
HTH!