Here is how expressing works best for me:
If I wake up before the baby in the morning, I express a bit from one breast then. If not I do it after feeding
Then I do a little bit more during his mid morning nap (unless he insists on sleeping in sling or i have somewhere to go)
If he only feeds from one breast I pump a bit from the other unless I am not at home.
If I want to go to bed early I pump as much as i can at 9pm and up to bed I go, along with the morning expressing this is usually enough to make a decent bottle, OH does a feed sometime between 10 and 11 and changes nappy and gets LO ready for bed and brings him up and settles him (he is still in our room at night). So I can sleep from 9.20 till about 3.30am. In return for this, if LO is wanting to get up at 6 to feed, I take him downstairs so that OH can sleep in peace until he needs to get up for work.