I've had xp professional for years now and my 5000MD always worked fine with metallics and white (in spot color mode), and the dye sub worked fine, too. The driver I used was downloaded from the ALPS site before it went down and is a zip file called MD224XP. It's their last one, I think. You have to set the ALPS as the primary printer on a parallel port. I have the usb kit but I remember I couldn't get it to work, so I went back to the parallel setup.
I don't think any color would show up good on a black background. I've always used Papilo PAS/2 clear paper with the ALPS. Even then, if I didn't print a white background first, none of the colors would show up on a black background. So, my solution was always to print the image in white, lay the decal down, and then print another image in color and lay it on top. After sealing, you can't really tell it's double decals. You can also print the image in white, then run the paper back through and print the color on top of the white. Tried that a few times, but the 2 decal method seemed to always work better. The ALPS resins can be printed on top of eachother, but sometimes it would remove the white base and leave a small hole.
Printer inks, even laser color printers printed on clear paper would not show very well on a black background, if at all. You could print the image on white decal paper and cut it out, or have someone print what you need with an ALPS.