I presume the video/mpeg is what you are seeing on the samsung - this is because the file is being transcoded. Your NAS probably hasn't the CPU grunt to transcode video (particularly if it's HD) on-the-fly - it can't keep up. Suspect it's not Serviio version related, but rather you're playing a higher level MKV file (not all MKV's are created equally).
A few options:
- Turn off transcoding and see if the video plays. You haven't mentioned what profile you are using but you should be able to modify it to remove transcoding for this type of MKV (use MediaInfo to find out exactly what the video and audio streams are) or to change it from transcoding the video to simply remuxing it (and seeing if that works);
- If its only a few files, you can permanently transcode them to a playable format.
Have a play with it - if you need further help post MediaInfo details for the file that is failing and let us know the renderer profile you are using and whether the file plays if the profile is changed to the "Generic DLNA profile".