Headaches are so short term that even if you cast a spell, it would never take effect in time.
There are many methods of soothing a headache beyond the pain relief medication, many depend on what kind of headache you have.
A tension headache can be relieved by taking a hot, calming bath as well as some sleep.
A migraine or cluster headache can often be helped (not fixed), by staying hydrated and lying in a dark, quiet room.
A light sensitivity headache is often improved by lying in a dark room.
Dehydration headaches can be improved, simply by drinking.
Eye strain can also cause headaches, so staying away from phones, computer screens or televisions is always a good idea.
But as always if you have a medical concern, or the headaches are frequent or last for long periods of time, it is recommended to speak to your primary doctor.