5) Joke about how early it is....:my coffee hasn't kicked in yet, so I can't think of a good pick up line"
4) Comment on the music playing. If it's something good, ask if they know who the artist is...even if you already know.
3) Give them a compliment, but try to make it coffee-related...."I don't know how you can look so great before you've had coffee"
2)Comment on their Order. If they order before you, then you have the option of lying and telling them you're getting the same exact thing.
1) If they are in line behind you... pay for their order..." you look like a nice person"....it'll start a conversation. And she will remember it for months.