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The most famous Captain America continues to be Steve Rogers, the only man whom the super-soldier serum didn't corrupt, at least in the MCU. Every fan knows that Captain America's weapon of choice is his shield that helps in knocking out his enemies and when thrown, returns to its rightful owner.
Even though Steve Rogers is the best-known person who has wielded Captain America's shield, he isn't the only one, not by a long shot. Just like with Thor and his hammer, multiple characters have at one point either become the new Captain America or at the very least used his shield and achieved many great things with it.
5 Isaiah Bradley
One of the things that the MCU did right in Falcon and the Winter Soldier was bringing Isaiah Bradley onto the scene as Bradley deserves more recognition than he has gotten so far. His backstory in the comics is complicated and sad. He was one of the many African-American soldiers the American government experimented on in order to create another super-soldier. Unlike many of his friends, Bradley survived the experiments and began fighting for the army.
However, when he put on the Captain America suit and took the shield with him, he was punished for it and sent to prison. Isaiah Bradley's story is a good example that even people who have the best of intentions (as Bradley who just wanted to help people did) can be unjustly pursued and ostracized by others.
The good news is that at least Isaiah's grandson Eli got to wear the costume and use the shield when he joined the team the Young Avengers - and this time around, Eli got to show he was just as worthy of wielding the shield as his grandfather.
4 Bucky Barnes
Steve Rogers' best friend and ally Bucky Barnes was a natural choice as to who should become the next Captain America. And Bucky did wear the costume and fought with the shield for a time. Bucky took on the role of Captain America in the difficult times when Steve Rogers was presumed dead, and he performed admirably in his new role, as he's previously undergone rigorous training and was a capable fighter.
In the MCU, Bucky also proved that he was able to fight with the shield, even though he didn't become the new Captain America after Steve Rogers' retirement. Instead, the shield and the uniform went to...
3 Sam Wilson
Alongside Bucky Barnes, Sam Wilson is one of Steve Rogers' closest friends, and he fought by his side many times in the comics, as well as in the MCU. Also known as the superhero Falcon, the MCU version of Sam Wilson doesn't have any special powers, unlike his comic book counterpart. However, that didn't stop him from taking the shield in the end after the old Steve Rogers had asked him to be the new Captain America.
After his initial justified reservations about stepping into the Captain America shoes, Sam took on the role and proved that he could fight with the shield just as well as his friend even though no super-soldier serum is running through his veins.
In the comics, Sam became the new Captain America as well and joined the Avengers. He maintained the role even during the now-iconic, initially controversial series Secret Empire in which Steve Rogers was revealed as Hydra's secret agent.
2 Peggy Carter
Agent Peggy Carter, portrayed by Hayley Atwell, is one of the fan favorites of the MCU. Even during World War Two when women didn't have as many rights and opportunities as men, and after, Peggy managed to build a respectable career for herself and helped save the world many times. However, she made just as good Captain America under the right circumstances.
A good instance of this was shown in the first episode of the animated MCU series What If...? in which Peggy Carter is the one to receive the super-soldier serum rather than Steve Rogers, fights in World War Two, ends up in the future, and goes on to defeat Ultron alongside other heroes, such as Thor.
The comics also saw Peggy Carter wield the shield, more specifically the storyline Exiles. And considering Peggy's intelligence and bravery, if she continued being Captain America in the MCU, she would have no doubt done a wonderful job.
1 Clark Kent
In one of the most epic Marvel/DC crossovers, none other than Clark Kent aka Superman wielded the shield. Even without the shield, Superman is a force to be reckoned with, but with it in his hands, he was even more impressive. It happened in the crossover JLA/Avengers that came out in 2004. The two superhero teams had to work together to find hidden totems and save the universe.
At one point, the superheroes take on their biggest enemy in the fight, and in order to win, Captain America borrows Superman his shield to help him. Not only that but Superman also wields Thor's hammer at the same time! Superman is usually a being of high moral integrity, so if any DC superhero deserves to wield the shield, it's him.