Arghhh, I totally hate vectors too...it's one thing when all you have to do is find the vector equation of a line, or calculate magnitudes and scalar products of vectors...but entirely another to use this to prove random geometric properties...
It sometimes helps to list out the different kinds of questions they usually ask, and outline the method you need for each...the usual ones are things like finding out whether two lines are parallel/skew, finding the point of intersection if there is one, finding the angle between two lines, etc...(although I'm not entirely sure about Edexcel, of course).
Just practising questions is definitely the best idea...