Thanks. That sounded simpler, but definitely wasn't simple. For other people attempting to do this, if you want to add a
@shortcut to the extension, if you're not logged in as Admin (which I hope you're not usually), you need to go to Program Files (x86)/WinSCP/Extensions (or wherever you've installed WinSCP), locate the extension in question, right-click it and go to Properties, go to the security tab, assign yourself (the user you log in as) Full Control, then OK out. Then right click the Extension filename and select Edit from the context menu to open it in the powershell editor.
There, you can add the line
or whatever other shortcut you like, from the list allowed on this page
https://winscp.net/eng/docs/custom_key_shortcuts and save it. It sure would be nice if the extensions syntax page linked in the above post made it clear that the way to specify Ctrl+0 was simply to say
Ctrl+0, though. This shortcut will take effect when you restart WinSCP.
I assume it's good practice then to go back and remove the Full Control & Modify permissions from your user.