I've looked those words up on several dictionaries. Firstly, 使う and 遣う have the same meaning for the most part, but there is a difference. 使う is used for the word つかう in general because it is easier to write and read. 遣う is used in specific situations: to say 'use your head a lot', to say 'use money', and a fancy way of saying 'use tricks or skills very well'. Secondly, a few dictionaries show only 気を遣う for きをつかう, and some say 気遣う is only used for きづかう. But others don't refer to these differences. So, I think 気を遣う is more correct, but 気を使う is also OK. I think 気を使う is just a substitute for 気を遣う, but sometimes some people might choose to use 気を遣う to emphasis something because there is actually a small difference between 使う and 遣う.