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Heat butter in large Dutch oven over medium-high heat. When foaming subsides, add broccoli, onion, garlic, dry mustard, cayenne, and 1 teaspoon salt. Cook, stirring frequently, until fragrant, about 6 minutes.
Add 1 cup water and baking soda and bring to simmer. Cover and cook, adjusting heat to maintain simmer, until broccoli is very soft, about 20 minutes, stirring once during cooking.
Add broth and 2 cups water and increase heat to medium-high. When mixture begins to simmer, stir in spinach and cook until wilted, about 1 minute.
Transfer half of soup to blender, add cheddar and Parmesan, and process until smooth, about 1 minute. Transfer soup to medium bowl and repeat with remaining soup.
Return soup to Dutch oven, place over medium heat and bring to simmer. Adjust consistency of soup with up to 1 cup water. Season to taste with salt and pepper. Serve, passing extra Parmesan separately.