Place 1/3 cup barley in a blender; process until coarsely ground (about 15 to 20 seconds). Place ground barley in a large saucepan. Repeat procedure with remaining barley. Cook barley over medium heat 4 minutes or until toasted, stirring frequently.
Add water, milk, honey, and salt; bring to a boil. Reduce heat; simmer 25 minutes or until barley is soft, stirring frequently. Add cheese, chili powder, and chiles; cook 5 minutes or until cheese melts, stirring constantly. Top each serving with 1 tablespoon sour cream. Serve with hot sauce, if desired.