Prep all ingredients: dice onion and bell pepper, mince garlic, drain and rinse beans, measure spices and liquids.
Set Instant Pot to Sauté mode on High. Add olive oil and ground beef. Cook 4-5 minutes, breaking into crumbles, until browned. Drain excess grease if needed.
Add onion and bell pepper to pot. Sauté 3-4 minutes until onion is translucent. Add garlic and cook 1 minute more, stirring constantly. Stir in tomato paste and cook 1 minute to caramelize.
Pour in beef broth and Worcestershire sauce. Scrape the bottom of the pot thoroughly with a wooden spoon to deglaze and prevent burn notice.
Add fire-roasted diced tomatoes, crushed tomatoes, kidney beans, pinto beans, and all spices including chili powder, cumin, smoked paprika, oregano, garlic powder, onion powder, cocoa powder, brown sugar, salt, pepper, and cayenne if using. Gently stir to combine without disturbing bottom layer.
Secure lid and set valve to Sealing. Cancel Sauté, press Chili/Bean or Manual/Pressure Cook on High, and set timer for 20 minutes. Allow 10-15 minutes for pressure to build.
After cooking, allow natural pressure release for 10 minutes. Then carefully quick-release remaining pressure by turning valve to Venting. Remove lid once float valve drops.
Stir chili and season to taste with additional salt or chili powder. Let rest on Keep Warm for 5 minutes to thicken before serving with your favorite toppings.