No longer displays on desktop - Chrome 89+
The support for the Web Share API has been added to desktop as of Chrome 89. Therefore the polyfill no longer displays on desktop in Chrome/Edge.
The issue is the Windows equivalent isn't as great as it is on iOS and Android and lacks the ability to share on social media like in the polyfill.
Is there any way of utilising the polyfill rather than the native API? Can it be manually evoked via JS?
I don't think there is an option for that. As you can see here the polyfill is a fallback to navigator.share. So if navigator.share exists, then the browser's implementation is used and not the polyfill. Well, that's the definition of a polyfill I guess.
The Web Share feature in recent Edge and Chrome versions for Windows also appeared to me as really limited, there doesn't seem to be an option for sharing on social media which is arguably the most popular way to use it nowadays. However, this is because you might not have a Windows app for any social media installed and that supports sharing. The Twitter app in the Windows Store offers sharing. If you click on "Get apps in Store" I think you get a list of apps that support sharing.
You might be able to do
navigator.share = undefined
before importing the polyfill.