Nope, it's pretty straightforward:
1) Go Invisible or Stealth (make sure it says "Hide in Shadows Succeeded")
2) Don't let your character attack or talk to anyone (this will make them visible)
3) Get behind Mr. or Ms. I'd-like-to-have-a-dagger-stuck-between-my-kidneys
4) Grin like a maniac and go for blood
5) Run away and, if possible, repeat.
There are some enemies that are completely immune to backstab--chances are, you haven't met them yet. There is also a Thief that cannot Backstab: The Swashbuckler. But you say you're using Jan, and Jan isn't a Swashbuckler, so that's not your problem. I'd say that you either have a bug, or you think that Jan is Hidden when he really isn't--as I recall, Jan's Hide in Shadows and Move Silently skills aren't that high. Jan's Strength is pretty weak, too--that makes his Backstab less likely to hit the target. Not that I'm saying Jan is a bad Thief, heavens no, he's just not made for Backstabbing--that's what Yoshimo's for.
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Volothamp's Comeuppance
Everything you ever needed to know about the entire Baldur's Gate series......except spoilers.
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