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First you will need to sand the trim to dull the finish so the primer will have something to stick to. Then you will need to wipe it downwith mineral spirits ( paint thinner) and then wash with amonia and water as this will make sure the surface is clean.
I primed my trim Duron Alkyd Enamel Undercoater and this takes 24 hours dry time before you can apply finish paint, but if you want to or need it to dry faster you can prime with Zinsser BIN. The finish paint should be an acrylic semi-gloss(I used Duron Plastic Acrylic Semi-Gloss) or gloss depending or your taste. I would not use an alkyd/oil based finish paint as they all yellow and alot don't work all that well. You most likely will need to apply 2 coats of finish paint to get even coverage over stained woodwork.
Enjoy the new look.