Ayurveda doesn't work fast, which is the downside, but it works naturally along with your body. I don't have my book with me, letting another person borrow it.
Take a large metal cooking spoon, pour 1 tsp of ground black pepper in it. Add water to make thin paste. Heat over open flame on stovetop till it bubbles. Let cool enough to touch. Spread on headache with fingers. i heard this came from Srila Prabhupada.