Yes, peppermint is VERY effective for headaches if you apply it as the headache is starting. It does burn the skin a wee bit if applied directly, but usually only for a moment or two. Don't   apply too close to the eyes. You can also add it to almond or    olive oil to dilute it slightly...
It is also effective to merely inhale the peppermint essetial oil from the open bottle and this works well for the nausea that    accompanies some headaches...

I agree remaining hydrated by drinking plenty of water should help; most of the headaches I get start because I am dehydrated...coffee, black tea, soda, juice; these do not hydrate!   Water and herbal   tea are best.