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Caffeine causes all your blood vessels to contract. It's one of the reasons it raises your blood pressure. It can also therefore restrict blood flow. It also makes your hands and feet cold because it's restricting blood flow which is why it's really a bad idea if it's cold outside to drink coffee to warm up.

On the other hand cayenne pepper is a vasodilator and it opens your blood vessels up. It increases your blood flow which is one of the reasons it makes your skin feel warm. If it's cold outside and you want your hands and feet to feel warm then sprinkle a tiny bit of cayenne pepper in whatever you're drinking and it will increase the blood flow to your hands and feet and they will feel warmer. You'll also lose more body heat to the cold because of this so don't do it unless you're dressed warmly and you're protected. This is not something you want to do in a survival situation because you'll lose a lot of body heat.