When I want to change to a second custom skin it asks which body style I want.
The thin arms version shows the new skin I have selected, the thick arms version shows the previous custom skin.
If I want to use the thick arms body style my old skin is chosen so I have to choose thin arms.
If I want to add a 3rd custom skin, the body selector shows both previous custom skins and I cannot use the new skin unless I close minecraft and restart.
Workaround by [~Auldrick]:
I found a better workaround for this. While the body type selector is being displayed, minimize the game window to the taskbar. When you restore it, the body type window will be rebuilt with your new skin in both positions.
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[MCPE Mod] Auldrick: Does that mean that when I name the skin custom.png. The bug happened?

Chandler: No, it doesn't matter what you name your custom skin file. When you import a custom skin, the game saves a copy of it internally, and that copy is always named custom.png. (This isn't new; the game has always done this.) The point I was trying to make was that because the game always uses the same file name internally, each imported skin overwrites the previous one, so it's not currently possible to import different custom skins for different characters.

oof. Why can't we have multiple custom.png files (e.g: character1.png, character2.png, etc•)

I imagine we could, and I'm hoping Mojang will take the initiative to make it happen since it seems like an obvious ask. If they don't, we can still ask for it on the Feedback site.
Confirmed on Windows 10 1.13.0.
Minecraft currently doesn't support importing multiple skins from images files. As in past releases, an imported skin file is saved to the file custom.png in the com.mojang\minecraftpe folder. The Character Creator now makes it possible to have up to 5 custom skins in the user's Profile, but they all take their image from the single custom.png file.
Steps to reproduce:
In the profile, select an unused character and click Create Character.
Select the Classic Skins tab.
Expand the Owned section and click Import.
Click Choose New Skin.
Choose a skin file and click Open.
The "Skin Type" panel is shown to let you choose which model to use with your skin.
Expected results:
The selected skin file is applied to both models, and whichever one you choose is saved in the character slot.
Actual results:
If this is the first time you've imported an image (i.e. there is no custom.png skin file), it is applied to both models and you can choose which one you want. However, if you previously imported a skin image, whether for the same or a different character, the custom.png image is applied to the model you chose when you imported it, and the newly selected image is applied to the other model. Whichever model you choose determines the image saved for this character as custom.png.