Captain America serves as an experienced Avenger and mentor within the anime, acting as a core member of Earth's Mightiest Heroes. He spearheads missions combating Hydra and the Masters of Evil while dedicating significant effort to training younger superpowered individuals.

After Hydra's defeat at a critical facility, Captain America endorsed offering sanctuary to three genetically modified teenagers—Makoto, Adi, and Chloe—following their defection. These teens, raised to view the Avengers as villains, recognized Hydra's true nature during their first mission. The Avengers provided them refuge and training to become the Future Avengers. Captain America directly shaped their development, overseeing combat exercises and instructing them in strategic thinking. He evaluated their performance during field assessments, including an unexpected attack by Ares on Avengers Tower.

His leadership extended to major operations. He assisted in securing Red Skull's prison transfer when the Winter Soldier attacked and joined missions investigating Hydra's Emerald Rain Project, linked to Makoto and the others' genetic modifications. During an intelligence-gathering mission concerning this project to the hidden city of K'un-L'un, he accompanied Thor and the trainees. The group faced an attack by Enchantress there, creating another practical training scenario. Captain America also engaged directly against threats like Ares and Ezekiel Stane's forces, demonstrating tactical command.

In the second season, amidst the Terrigen Mist crisis generating new Inhumans, Captain America continued leading both the Avengers and Future Avengers. He worked to manage escalating tensions between humans and the Inhuman royal family, participating in efforts to prevent open conflict. His operational role remained consistent across both seasons, focusing on mentorship through active field leadership.