probably depends more on whats in the basecoat, it isn't purely paint pigments, it has other things in it that cause the reflections, not to mention if it was a single stage black it would have clear mixed in with the base also.
but i would say that yes, that black basically gives more distinct reflections because you are looking at something with a background that isn't reflecting either.
i think the simplest way to explain the difference between black and white, is that the white washes out the reflections.
ie, black absorbs and does not reflect as much (or up to 95%, technically most paint codes for black have more than just black, ie, 202 toyota black has a very tiny amount of yellow in it. and codes for other blacks will have some blue or red, etc.)
but white itself reflects all.. the problem is that white that is so finely polished will appear... clear. reflects all colors but appears clear because there are no imperfections to cause the light to ounce around in. like how a block of ice that has no impurities in the forming looks clear, but a block of ice that has all kinds of imperfections and air bubbles will look almost white, the diffusing of the light source causes it to bounce around, looking white because it's reflecting all the colors and absorbing none.
the white paint of your car has titanium dioxide in it. the surface of it is trying to reflect all light sources back, but the rough and pitted porous nature of it at a microscoping level is causing the light to bounce around and diffuse on its surface rather than reflect, which is why it appears white instead of clear. your clear coat is actually white mostly, but so uniform and polished that it looks clear. if you were to scratch up the surface, it would then look white from the light being diffused on the surface.
which is back to why black makes a better mirror. the less light being diffused the better the reflected image from the clearcoat is