Do you only have problems with first impressions, or do you have problems with relationships in general? You mention that you're fine talking on line to people. This suggests that it's probably, as ilrein metioned, a voice or body language issue. Confidence is the key in both those areas, but only confidence to a degree where you can "back it up". Just be yourself, in other words. Act natural and get in the flow.
Also consider the fact that maybe people aren't judging you as harshly as you think. How much of what you're saying is an accurate picture of what people think about you, and how much is just you over-analyzing the situation?
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