Cream butter and sugar together in stand mixer on medium-high to high for 5 minutes.
Meanwhile, combine flour, baking powder, baking soda, salt, and vanilla in small bowl.
Turn speed on mixer to medium. Add eggs, one at a time, to bowl. Let mix for 30 seconds before adding next egg.
Turn speed on mixer to low. Add 1/3 flour mixture. Add 1/2 cup buttermilk. Add second third of flour mixture. Add remaining buttermilk. Add remaining flour mixture. Let mix until just combined.
Divide batter into four bowls. Add coloring to each and mix with a spoon until combined. Layer batter into bundt cake pan, one color at a time.
Bake for 50-55 minutes until cake tester comes out clean.
Let cool for one hour on cooling rack with opening facing ceiling (batter side up).
Twinkie Filling
Invert cake - using cooling rack to help - to make sure cake comes out of bundt pan. Once it does, flip back over and create 8 equally-spaced holes in bottom of cake using round nozzle or thin knife. Using your fingers, gently create a tunnel between the holes in the middle of the cake.
Combine marshmallow fluff/creme, butter, and vanilla in stand mixer until fully combined.
Add filling to piping bag fitted with round nozzle. Pipe into each hole, piping until cake begins to puff up slightly.
Vanilla Frosting
Combine butter, confectioners sugar, and 2 tbsp. milk in bowl of stand mixer on medium high.
Add vanilla. Add milk, 1 tbsp. at a time, until desired consistency is achieved.