Thanks to everyone for suggestions. In the end, I deleted Calibre and all my appdata personalisations (made a notepad file of all of them, plus screenshots, so come All the Apocalypses I can recreate ad infinitum). Reinstalled Calibre 4.22 & there is - thanks goodness - only one icon in the taskbar. It's seriously a first world problem (OMG I have TWO icons), but I'm feeling curiously soothed now it's working properly.
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