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Prepare baking sheet for cooling: Line a baking sheet with parchment paper or a silicone baking mat.
Make the glaze: Add the brown sugar, cinnamon, salt, vanilla, water, orange zest, and cayenne to a medium skillet. Place the skillet over medium heat and cook, stirring often, until the brown sugar melts into a bubbling sauce, about 1 minute.
Add the nuts: Stir in the pecans so that the brown sugar sauce coats them. Cook, stirring the entire time, until the pecans look candied and smell nutty, 2 to 3 minutes. As the nuts heat up in the pan, the sauce will slowly coat them and turn shiny. Watch closely as the nuts cook so that they do not burn. If the glaze starts to get thick and grainy before coating the nuts, add a teaspoon or two more water and keep stirring to help the sugar re-dissolve and give you a smooth, even glaze that coats every pecan.
Cool them: Transfer the candied pecans to the prepared baking sheet and spread them out in one layer. Allow the pecans to cool down and break them up before serving.