Mail app keeps throwing Horde_Mime_Exception after PHP & Mail limits adjusted (Nextcloud AIO)

Can you please post the full raw log message. The stack trace is needed. Instructions for doing so can be found in the support template.

  1. Should lowering mail max_message_size skip already-existing large emails automatically, or is manual intervention required?

Neither – there is no such configuration value.

See the Admin Manual section entitled: Groupware->Mail->Troubleshooting->Get account IDs.