The colour which sits directly opposite another colour on the colour wheel will make that colour really pop when placed together. As an aside, when you mix them, as in art, or make-up one will cancel the other out. That is why green concealor banishes redness in your skin. Purple will bring life to sallow skin and apricot will disguise spider veins or tired rings from under your eyes.
Blondes are going to look great in purple.
Red heads will look great in blues or greens depending on the depth of their hair colour.
Brunettes will rock blues and greens depending on the undertone their hair throws. If their hair has more coolness to it, as it blacks and cool brunettes, you will suit shades of emerald green. If your hair has copper or auburn highlights and dimensions to it, the blues will be your best friend.
Complementary colours are those colours that make something pop. They complement and the result will be complementary.
To discover more on how colour can work for you get my Every Woman’s Guide to Personal Colour