I generally will use a dark color with a strong middle value color for this kind of situation, but if you choose NOT to use a dark color as your second color, you can get some interesting atmospheric effects as well. Try playing with lime green and pink, for example. These colors are not great for type, however, so that needs to be factored into your color choices.
You have several choices in colorizing the photos. Assuming you have picked your spot colors (Let's say black, purple, blue or other darkish color plus some PMS Red):
1) Create duotone in Photoshop, using the curves to control color saturations
2) Create a DCS 2 file in Photoshop, using "edited" color plates for each color (so you could punch up a certain area with more color, for example)
3) In Quark, select the grayscale tiff, and assign it a PMS Red tone, leaivng background to white or none. You get a tinted picture.
4) In Quark, select the grayscale tiff, and assign image your dark color, and background of the image box as PMS red. You get a picture where the foreground is your dark color, but background is inverse, in color. A little like a solarization, depending on colors and image.
5) In Quark, select grayscale tiff, set image to Red and background to your dark color. You get a stranger image, like a negative on color, which might work, depending on your colors and how you're using the image (content-bearing or atmospheric).
In addition, you can play with the contrast controls (the line graphs) to achieve solarization effects, etc. Any of the Quark effects can also be done in Photoshop, if you prefer the software controls there.
Hope this helps.