Exposure is applied to the full image equally shadows, midtones and highlights. Brightness will have the most effect on the midtones and shadows but little effect on the highlights.
I hate to disagree w/ the experts here, but I don't believe this explanation of the exposure slider is strictly true. In my experiments (and as shown in the user interface), the exposure slider affects the 3/4 tones and the highlights much more than the mid-tones, shadows and 1/4 tones. All of the tonal sliders have some affect on all of the tones, but I find it useful to think of their
primary affects as follows:
Recovery: The upper 10% or so (highlights)
Exposure: The 3/4 tones
Brightness: The mid-tones
Shadows: The 1/4 tones
Blacks: The lowest 10% or so
There's significant overlap between the sliders, as none of them have a sharp cutoff, but they each have less affect as you move further from their primary zone. In use, I tend to adjust the tones of the image that need the most adjustment first, using the slider that's closest to those tones, and then tweak the others as needed. So, to get back to the OP's question, if the image seems to need adjusting most in the 3/4 tones, I would start by adjusting the exposure; when the 3/4 tones look right, I would then focus on the mid-tones and adjust the brightness as needed. I would do the reverse if it seemed like the mid-tones were most in need of adjustment. Sometimes it may make more sense to start w/ the shadows, or the highlights. Try working that way for a few images and I think you'll get a better feel for what the sliders are actually doing. My $.02 worth. Cheers,