Since this seems like a really big sticking point for a lot of aspiring PUA's I thought I would post my favorite way to go for that first kiss. It's something I started using after I had a chick kind of lead me into it once.
First you need to be holding her hand. The easiest way to do this is to be walking by her side and let your hand brush up against her's and linger for a second. If she is into you, she will take your hand. When she is holding your hand walk with her, or if you are standing next to her, play with her fingers with your hand, while talking to her.
*If a chick will take your hand in a "I am attracted to you" manner, she is only a hop, skip, and a jump away from being ready to kiss you*
Slow down the conversation. You want it slow and relaxed.
Then if you are walking, stop and pull on her arm so that she turns and is now facing you. Then take her other hand, so you are holding both of them. At this point you should be saying something, hopefully funny, or at least just finishing up a sentence. You can also just trail off what you were saying. Look her in the eyes, then pull both of her hands around behind your back so that they are resting in the small of your back (You're still holding her hands. She should lean into you or step your direction, but don't be afraid to take a small step in her direction, while still looking her in the eyes). Hold the look for a moment, then tilt your head slightly and lean in. She should either come forward to meet you or close her eyes and tilt her head for the kiss. Then you go in.
The reason I like this technique, is that it is something that you can physically control, and yet it seems very romantic and spontaneous to the woman. Not only that, but it gives her a little more power because of her hand contact with your body, thus it cuts down on a lot of the potential awkwardness of you invading her personal bubble in the lead up. Finally, it allows you to gauge her receptiveness with many places to eject.
1) She doesn't take your first hand.
2) She doesn't allow you to take her other hand.
3) She doesn't hold your gaze or pulls away / starts a new conversation hurriedly.
4) When you start to pull her in, to wrap her arms around you, she resists or lets go of your hand.
5) You go in for the kiss and she turns away.
At any of those points you can eject with relatively little awkwardness or embarrassment.
Finally, if you follow the directions, there will be no doubt in the woman's mind where you are heading, without you having to say a word.