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In a large microwave-safe bowl combine dark chocolate pieces and shortening. Microwave, uncovered, on High 1 1/2 to 2 minutes or until chocolate melts, stirring every 30 seconds.
In a small bowl combine the 2 teaspoons chili powder, the cinnamon, and the 1/4 teaspoon crushed red pepper. Stir spice mixture into the melted chocolate mixture.
Slightly crush the popped popcorn; stir crushed popcorn into the spiced chocolate mixture. Stir until the popcorn is evenly coated. Using two spoons, spoon popcorn mixture into 20 mounds onto parchment or waxed paper. Drizzle tops of the mounds with melted white baking chocolate; sprinkle with additional chili powder and/or crushed red pepper.
Let stand 3 to 4 hours or until completely set before serving.