Preheat the oven to 250 degrees F. Generously coat a baking sheet with cooking spray. Toss the popcorn and pecans on the prepared baking sheet. Transfer to the oven while preparing the syrup.
Combine the brown sugar, butter and honey in a medium saucepan over medium-low heat; cook, stirring occasionally, until the sugar is dissolved and the butter is completely melted. Increase the heat to high and boil, stirring constantly, until thickened, about 4 minutes. Remove from the heat and stir in the chile powder, baking soda and 1 teaspoon salt. Remove the popcorn mixture from the oven; slowly pour the syrup over the top and gently stir to coat.
Return the popcorn to the oven and bake until the caramel is dry and hardened, stirring halfway through, about 1 hour. Let cool on the baking sheet.