Cook rice according to package instructions. Meanwhile, gently pat shrimp dry with paper towels. Heat a wok or large skillet over high. Remove pan from heat and carefully add 2 tablespoons oil and broccoli. Return to heat and cook, undisturbed, until crisp-tender and browned in spots, 1 to 2 minutes. Add 2 tablespoons oil and shrimp and cook, stirring frequently, until shrimp are opaque throughout, about 2 minutes. Remove from heat, add chili-garlic sauce and remaining tablespoon oil, and toss to coat. Stir in 1 to 2 tablespoons water to thin, if necessary. Serve with rice.