As many have pointed out one of the main causes for headaches is the blood vessels around your heat. They can either be too much widened or too much narrowed. Caffeine counteracts them being widened, alcohol counteracts them being narrowed.
Some pain reliever work better in combination with caffeine too and often there are variants that have a dose of caffeine to make use of that effect.
Still, recommendimg either is trial and error, so you might end up with even more severe headaches. Best is to drink two big glasses of cold water and wait some time if the headaches go away. Hot or cold packs induce similar effects on the blood vessels and can help reduce the pain before administering any form of drug.
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