CSPs and BP stuff can be found in the stickied tutorial at the top of this very forum section. The only difference is that you'll need to create new CSP and BP slots for these new costume slots. The easiest way for BPs is to just copy and paste one of the existing Battle Portrait files, then rename it with the number following the last BP for that character. So let's say Mario has BP 00, 01, 02, and 03. I just added a 4th costume slot, so I would copy one of those, past it and rename it to 04. Then I open it in Brawl Box and right-click replace the texture I want to use.
For CSPs it's a little different. When you have that character's CSP portraits open in Brawl Box, right click on the red file, the one you expand to get to the Textures folder they're located in. (Mario's is called MiscData0) Right click that red file and click "Import" then "Texture" Then find the CSP you want, add it, and rename it to correspond with whatever costume slot you just added.
Sorry if this all sounds confusing. It'll make a lot more sense if you read that stickied CSP/BP tutorial.
CBliss is pretty complicated and difficult to use. I would recommend cutting your teeth on just regular ol' costume replacement before you start using it. It's given me nothing but headaches hahaha.
You CAN technically use 14 costumes (I thought it was only a max of 12 for some reason), but once you go past 10 costumes, you begin overwriting the character after the one you gave all those costumes to. I'm just going with a flat 10 costumes for each person.