I used to pump immediately after feeding. If he's doing a good job of emptying you, you might not get much the first couple of days, but you should start seeing an increase in your supply.
I've heard some moms suggest pumping one breast while he's feeding on the other one. They say it gives extra stimulation which causes and increase in production. I never tried it myself, but what could it hurt?
Definitely pump after the morning feedings. For some reason, our bodies generally produce more in the mornings.
If you haven't already introduced the bottle, I would do it as soon as possible. There seems to be a trend of mom's not introducing the bottle during the first couple of weeks and waiting until they go back to work. Both my kids were introduced to the bottle (of breastmilk) before they were a week old, and they never had an issue.
Good luck!