I’ve always thought the long running “Multi-Account Containers” in Firefox was a better implementation of this idea than having to switch profiles and open a whole new window, when often what I need is a tab or two for a profile other than the one I’m in. You can even configure proxies to run on a per-container basis if that’s useful. But I can certainly understand wanting to better separate what your working on then just tabs with colored indicators to remind you which is which at a glance.
Those are useful but they lack the ability to have profile-specific history and bookmarks. I have a completely different set of bookmarks for Home and Work use and would never dream of mixing the two. Profiles are the only way to deal with that, but profiles are themselves difficult to work with.
Containers is not a replacement for profiles, they are completely separate use cases. Those who use multi-profile do so because they want separate bookmarks, settings, etc (e.g. personal profile vs work profile)... which containers cannot do.
In Firefox you can go to about:profiles to easily open new windows using other profiles. I bookmark that page with a keyword for quick access. (Also see about:about for a list of other handy 'about' pages)
A more classic-style profile switcher is available via the '-P' (or '-ProfileManager') command-line switch. If FF is in your $PATH you can run:
firefox -P
The '-P' switch can also take an argument of a profile name to open it directly.
But yes, it would be nice if at least one of these options were exposed in the UI so it was more discoverable by users.
That's not user friendly or works on all OS (eg: firefox -P). There are also other issues with Firefox profiles. For example, on macOS, using different profiles mess up Firefox's icons on the dock and profiles always open behind the current Firefox window.
There's no way around this. Profile support on Firefox is bad and it's a shame because they've had them for years.