Woo!
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This does, however, require that I disable the network and switch to 640x480 (If I want high color) or else the system complains and will not play video. This is noted in Diamond's Readme. Only real problem I have is that there is no left channel audio, but I suspect this to be the cable I used, the card may not use a normal pinout and this should be easy to fix with a multimeter to bell out the ground pins and a pin to move the crimped connectors in the plastic housing at the end of my cable.
Now, give me access to Vogonsdrivers and I shall upload the working drivers for those that need them in the future.
Edit: The audio bug, seems to be software as the CD passthru works fine and as such, I can be 100% that the pinout is correct. It might just be the way the file I tested with was encoded, the computer did complain about it a lot when it was encoding and VLC doesn't like it, plus I think I may have used non-standard parameters, so it is only fair to say the Scenic probably has no idea what I'm asking it to do. I have some old VCDs somewhere so perhaps I'll try those as I know they work, plus a lot of my old stuff used VCD encoding so I can try that too.
Edit 2: Seems the MPEG card didn't like having the CD-ROM plugged into it, despite the sockets being marked for this purpose. I have connected my CD-ROM drive back to the sound card and have connected the MPEG card to the AUX-IN that I wasn't using anyway, I prefer it this way regardless of how well it works - and it does work, so that's a bonus. Sound quality is actually pretty good, video is smooth, this was a good investment. Still haven't tried playing a real VCD from a disc yet, I shall do it tomorrow as I have to go to sleep soon and can't remember where my VCD authoring software is, nor can I be bothered to dig out any of those old VCDs I have as I seem to think they are stored in the bottom of a box at the bottom of a stack of boxes that are behind other stacks of boxes.