As far as I know, the new desktop, MS Store and Android versions do not have an offline cache for scrobbles, but on Android the official
Last.fm for Android app is able to scrobble VLC and provides an offline scrobbling cache which submits them when you have a WLAN connection to the internet again. You have to enable this in its settings of course.
There was a workaround for the old desktop versions 2.2.x though by using the foobar plugin from the offical Last.fm scrobbler desktop app v2.1.37. As the VLC audioscrobbler plugin did not work in these old versions, you had to use the foobar plugin anyhow together with the Last.fm scrobbler which provides an offline cache. The new Last.fm scrobbler app 3.1.28.1 does not support foobar anymore, so this workaround will no longer work. Last but not least the new VLC desktop version 3.0.3 works again with its internal audioscrobbler plugin, but I haven't checked if there also is an offline scrobble cache for it now.