Is there a way to get different profiles to show up as different program groups in Firefox for Windows?

Short answer: Sorry, no. All you can do is to edit the task bar settings and disable combining windows.

Long answer: The app window combining algorithm and Firefox's multitasking mechanism really leave you without much of an option. Windows groups apps based on a window ID. (I've forgotten the actual name.) So, it is possible for one process (say Firefox.exe) generate different window IDs. In fact, explorer.exe does that; that's why normal Explorer windows and Control Panel do not merge. Firefox.exe, however, does not. Quite to the contrary, it actively seeks to prevent multiple versions of the Firefox processes from launching and instead uses interprocess communication to have one Firefox process do all the heavy-lifting. Copying firefox.exe under another name and running it in context of another user account does not work. (I tried.)

Your only option (which is really not an option because of its difficulty) is to download the Firefox source code, modify it to have it implement different window IDs for different profile sessions, and then compile it.

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