Following https://www.reddit.com/r/PleX/comments/192jrf2/comment/n8vru67/?context=3, I’ve found that, when the media server has remote access disabled but custom server access URLs set up and an iPhone or iPad is “off network” (doesn’t have a direct connection), everything works as normal except attempts to download a video get stuck on “Queued”.
However, the Windows app doesn’t have this problem.
This can be fixed by ensuring that the custom URL has the port suffixed (:443), as suggested by another user at Reddit - The heart of the internet and verified by myself.
Separate from the custom access URL, PMS v1.42.1.10060 has a bug that can cause downloads and optimizations to stay queued.
If Settings → Transcoder → Maximum simultaneous background video transcode = Unlimited, then any downloads or optimizations that need transcoding will stay queued, and not be processed.
The workaround is to change the setting to anything but Unlimited.