1. Preheat oven to 425°.
2. Cook broccoli in boiling water 1 minute. Drain and plunge into ice water; drain.
3. Combine 1 1/2 teaspoons rind, juice, 1/4 teaspoon salt, and 1/4 teaspoon black pepper in a medium bowl. Add shrimp; toss to combine. Arrange broccoli and shrimp in a single layer on a jelly-roll pan coated with cooking spray. Bake at 425° for 8 minutes or until shrimp are done.
4. Combine oil, remaining 1 1/2 teaspoons rind, remaining 1/4 teaspoon salt, remaining 1/4 teaspoon black pepper, and crushed red pepper in a large bowl. Add broccoli; toss to combine.