I think it's dependent on your length and how sensitive the girl in question is. Most women find it easier to orgasm during penetration if she is on top or from behind as it's easier for her to control the depth.
All positions are great though even if they don't bring you to climax. The best bet is to just try out every position you can both think of - when she finds one she likes she'll probably want you to stick to that for a while.
grace86 is right that it varies from person to person. One standard suggestion is that the girl put a big pillow under her butt/lower back while in missionary. This creates a different angle and provides more penetration and more likelihood of hitting the g-spot.
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