I was rereading chapter 16 last night and I was struck by the contrast of Elizabeth's first 1 on 1 'interaction' with Wickham, compared with Darcy. Compare:
"Mr. Wickham was the happy man towards whom almost every female eye was turned, and Elizabeth was the happy woman by whom he finally seated himself; and the agreeable manner in which he immediately fell into conversation, though it was only on its being a wet night, and on the probability of a rainy season, made her feel that the commonest, dullest, most threadbare topic might be rendered interesting by the skill of the speaker."
With
"[Darcy] looked for a moment at Elizabeth, till catching her eye, he withdrew his own and coldly said, "She is tolerable; but not handsome enough to tempt me; and I am in no humour at present to give consequence to young ladies who are slighted by other men. You had better return to your partner and enjoy her smiles, for you are wasting your time with me.""
With these very different first impressions, it is no wonder that Lizzy is more receptive to Wickham than Darcy, despite the signs the author gives us that these first impressions may not be the full picture of either man.