Try launching calibre in debug mode from a command-line "calibre-debug -g" (without the quotes). If the plugin isn't initializing properly, there should be some kind of message printed there that might give a clue.
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I believe that there is something fundamentally wrong in my setup - but what?
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Don't dismiss the possibility that there's something wrong with the plugin.

It's been a very, very long time since I've installed the plugin fresh. I, and most others likely, have been only upgrading our KindleUnpack plugins for quite a while.
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P.S. Just found out that the corresponding java file (json) is missing in the "C:\Users\MyName\AppData\Roaming\calibre\plugi ns" directory. I have no clue with Java scripts ...
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That's not a java file it's a JSON file. That's where the preferences for plugins are stored/retained. It's normal for it not to exist until the plugin is run/configured for the first time (which yours hasn't).
EDIT: OK, well it doesn't seem to be anything
inherently wrong with the plugin, as I just installed it to a virgin installation of calibre (v2.37.1) and everything showed up on the toolbars selected as expected (and configuration worked) after a calibre restart. That debug output should prove enlightening when you get it.
Also it looks like you are you running Windows, but I can't be sure. Nevermind, you said Windows 10-duh

That info (and whether you're using an x86 or x64 flavor of calibre would be handy). Your icons look different, so I assume your using a new custom theme? If you could direct me to the one you're using, I'd like to install it and rule out the possibility that new theming functionality is somehow playing a role in this (since the plugin does supply its own icon resource. Thanks.
EDIT2: I matched the icon theme you had that doesn't seem to have any effect on a fresh install either. Unfortunately, I can't test on Windows 10 quite yet. I only have that on my employers PCs.