Depends entirely on what you're doing.
If you are running one processor-intensive thing at a time, and it does not take advantage of multiple processors (say, many Photoshop operations, or most of what iMovie does), then the 867 will be much faster.
If you are doing something intensive that makes heavy use of both processors (say, 3D rendering) then the 2X500 will probably be a little faster. Remember, though, that even under IDEAL circumstances, you lose a portion of the available power when running processes that use multiple processors, so it's going to be close.
If you are doing several tasks at once--say, compressing a video while surfing the web or working in another app--then the 2X500 machine will feel much faster, since it'll be able to more efficiently spread the work between the processors. A modern OS can do this sort of switching on a single processor, of course, but it works better with two.
It's also worth remembering that, assuming you're talking about the machines I think you are, the 867MHz one has a faster system bus, significantly better default graphics card, and a different cacheing system (the DP500 uses L2 cache only, while the 867 has faster, smaller L2 and larger, slower L3), all of which can be relevant (particularly the graphics) depending on what you're doing.
How about some real-world benchmarks, albeit on older applications:
http://www.barefeats.com/pm01.html
...and indeed, in FileMaker Pro (only uses one processor) the 867 is much faster, while in CineBench (heavy multiprocessor) the dual 500 edges it out by about 10%.
The closest thing to a good reference you're going to find are benchmarks at BareFeats, and maybe MacWorld (not sure how much of their results are aviailable online). You're only going to get comparisons of machines of similar vintage, though.