I want the username on my main account to be changed to the username on this account. Basically, if I were to purchase 1k robux on this account and on my main, what would happen if I changed the username on this account to something else and then changed the username on my main account to this account’s username? Would this work?
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When you change your username it’s still being held by the account, so if you tried to change it and then create a new account it wouldn’t work. Your previous usernames are “reserved” for you in case you want to change it back later. Hope it helps! 
So I can’t swap usernames with different accounts?
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No, you can’t. For reference,
( Changing Your Username – Roblox Support)
Once you set a username you own that username and no one else can get it, even if you change it later.