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For me, the shouldermon is any little pokemon that evolves and catches my eye that week. Based almost purely on aesthetics or pokedex entries, functionality doesn't enter the thought process at all. How do you find it? Imagine you are the character of the week in the anime or a protagonist in some terrible fanfiction, what would you want to share your story. Does it serve as a complement or a counterpoint to part of your personality? A 'bro' could fit here too, but not for me. In the past, it's been skiddo, magnemite, shinx and wooper. A shoulderman is powered by imagination and rises about things like "stats" or "viability".
An ace is a pokemon that you actively include on your team or in a TCG deck or whatever.
Not the unexpected friend but the ruthless gamewinningist motherfucker that you enjoy using, karenfags be damned. If you're thinking in story terms, this is the guy you pull out for climatic battles. This is the slot in your team reserved for powerful legends or mythic rares. This is the guy you are tempted to lie about 'always loving' because some sore loser is telling you "[ace] is bullshit" and you know because thats why you chose him.
A bro is the reliable core member of my team. They've pulled their weight in actual game play. Not only do these guys have memorable nicknames from their playthroughs, but there are stories. Mariel(The Azumaril) saved my ass at Viola's gym in my ground+fairy run and to end of the E4. While Sumoppet(The Sawk) was the main leveler and gym killer in my White Nuzlocke. If you can't feel like crying when a bro gets killed in a nuzlocke, step back and reevaluate if it's truly a brother in arms. You don't find a bro, a bro finds you.