Heat a large nonstick skillet over high. Sprinkle chicken evenly with salt, pepper, garlic powder, paprika, cumin, and cayenne.
Spray pan with cooking spray. Sear chicken over medium-high heat until brown but not cooked through, about 1-2 minutes per side. Remove chicken from pan to a plate.
In the same pan, lower heat to medium and add onion. Sauté until slightly browned, about 4-5 minutes.
Add in bell peppers and garlic. Continue to sauté until veggies are soft, about 5-7 minutes.
Mix in rice. Stir and sauté until rice is coated with mixture and slightly translucent, about 3-4 more minutes.
Add chicken broth, tomato sauce, and salt. Bring to a boil, scraping the brown bits from the bottom of the pan. When liquid is boiling, lay chicken on top of the liquid/rice mixture.
Cover the skillet, lower heat to medium-low, and simmer for 15-20 minutes, or until the rice is just cooked through.
Remove pan from heat. Stir the frozen peas and let sit for a minute to allow the peas to thaw.
Sprinkle rice with chopped cilantro and lime wedges, if desired. Serve one piece of chicken with 1 cup of rice mixture.