Here's my minor in Geology (B.S. Geography, 2002) advice. If you don't know much about rocks, you may want to stick to your fish supply store. If you don't know the difference between sandstone (ok) and limestone (bad) - don't risk it.
Generally, the easiest to identify, and safest for aquarium rocks are slates. Slate is easy to tell because it's typically dark in color (gray, to blue-gray, to black) and is many flat layers atop eachother. Slate is a metamophic rock derived from shale, which come from clay (clay--> shale--> slate--> schist--> gneiss). Shale is ok too, but tends to be flakey, and breaks too easily in some instances.
The viniger test is also not fail-safe. For a true test of calcium, you need something stronger, like HCl (Hydrochloric Acid).
If any of you have pictues of rocks in question, post them up and I'll try to help you out.
Edit: forgot this part:
Volcanic/Plutonic rocks are also a good choice. Basalt (dark-grey to black, produced by lava flows) is a good choice. Plutonic rocks such as granite, diorite and gabbro also are safe choices. Volcanic glasses (not to be confused with rocks) of obsidian and pumice/scoria are also safe (as I believe the article mentioned). Just beware of the pumice/scoria (or any rock) that has the vescules through it -aka a bunch of holes- as it is a place that can hold contaminates.