hey tara! i'm no expert but i can share my experience. i was told to pump right after the morning feeding, and that has worked out great. no oversupply issues at all. i went back to work pretty quickly, so DS had a bottle by the second week, for one feeding a day, 4x/week, and he still latches like a champ, so i don't think i've ruined him, which i was very worried about! your LO is probably old enough to handle a bottle every now and again without nipple confusion, but the general consensus is 6 weeks old i think.
I started pumping the day we came home from the hospital, which was the day after I had her. Reason was though, my milk came in that quick. I breastfeed exclusively but I pump sporadically through the day, depending on when she is sleeping. She usually nurses every 2 1/2 to 3 hours during the day and will go as long as 4 hours at night in between nursing sessions. I get my best pumping in at night. For instance, I pumped twice last night and got 4 ounces from each session ( 2 ounces per breast) and then nursed her about an hour after that. If I really need to pump during the day I will go take a shower to help with letdown, it does wonders. I've been focused on building up a supply since I am going back to school in August and I have a total of 65 bags of 4 ounces or more of milk in my deep freeze.
I introduced a bottle ( the Tommie Tippie, Closer to Nature ones) when she was 5 weeks and 6 days old. I had finals and had to finish a paper, so my dad got to give her the first bottle. She took to it well and we have had no nipple confusion. She gets a bottle about twice a week. Introducing the bottle was a hard thing for me to do emotionally but at that point I felt very confident that we knew what we were doing with the nursing, like you said.