It is more than color. You need the other beer to have a different density from Guinness, at least if you want it to stay separated for any length of time. And be careful which Guinness you use because there are a number of them out there with different "strengths". If the densities are too close, they'll mix together.
A good starting point in selecting interesting combinations is to look at the densities across different styles. Pick two that are widely different and find bottles of each. For instance, if you take a bottle of a kriek (red-looking fruit lambic), it would probably float nicely on most other beers, but you'd want to pick a nice, dark beer to show off the contrast (plus, if you used a kriek (cherry) or frambois (raspberry), pairing it with a porter or stout that has nice chocolate tones would taste very nice). Likewise, just about anything would float on a bock or a strong scotch ale like a "wee heavy".