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Just to clarify.
You want the KDE Connect app to have direct access to video files on your Samsung phone?
Is there a specific reason you can't just use the media browser on the phone and use the "Share" feature in that to send it to KDE Connect Send To Device?
There's a lot of them and I want to browse them from the file explorer on my PC. I'm sure I could accomplish the same by plugging the phone in, but I don't see the point in that when KDE connect already has the functionality I want.
Ah, I'm certain you can use sshfs from KDE Connect on your desktop to browse through the files on the phone. Depending on how the videos are stored, you should be able to find them on the Internal Storage drive. Unless it's DRM enabled videos, then it's locked down behind the app sandbox.
Are you using the play store version? I'm not entirely sure, but I think that Google restricted apps' access to storage from there. Maybe try the f-droid version?