Here's why:
* Superlative: The superlative form is used to compare three or more things and indicates the highest degree of a quality. "Most athletic" is already implied in the word "athletic" itself.
* Comparative: The comparative form is used to compare two things and indicates a higher degree of a quality. Similarly, "more athletic" isn't necessary because "athletic" already implies a higher degree of physical ability.
If you want to express a higher level of athleticism, you can use adverbs like "extremely" or "highly" to modify the adjective:
* Extremely athletic
* Highly athletic