Preheat oven to 250 degrees F (120 degrees C). Lightly grease a 10x15-inch jelly roll pan.
Combine egg white and vanilla in large bowl; beat until frothy. Add almonds and toss to coat. Pour almonds into a mesh strainer to drain excess liquid, 5 to 10 minutes. Return strained almonds to the bowl.
Stir white sugar, brown sugar, cinnamon, chili powder, and salt together in a bowl. Sprinkle sugar mixture over almonds and toss to coat evenly. Spread coated nuts evenly onto prepared jelly roll pan.
Bake, stirring every 20 minutes, until the seasoning clings to the almonds, about 1 hour. Allow to cool completely before storing in an air-tight container.
