Preheat the oven to 450 degrees F. Invert a muffin tin and spray the underside with vegetable oil cooking spray.
Stir together the baking mix, milk, and cayenne. Shape into a ball. Turn out onto a floured surface and knead 3 or 4 times. Divide the ball into 6 pieces. Roll each piece into a 6-inch circle. Place a dough circle over the back of each muffin cup. Press around the cup to form a bowl shape. Bake for 10 to 12 minutes, until lightly browned. Let cool slightly. Remove the biscuit bowls and reserve.
Brown the ground chuck over medium heat in a Dutch oven. Add the onion and green pepper and continue to cook until the meat is completely browned and the vegetables are tender. Drain off any fat and discard. Stir in the tomatoes, beans, chili powder, and salt. Bring the mixture to a boil, cover, and reduce the heat to low. Simmer for 35 minutes.
When ready to serve, spoon the hot chili into the biscuit bowls. Garnish with shredded cheese, sour cream, sliced green onions, and corn chips.