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The alpha is not a layer, but a channel. Windows > Channels and you'll see RGB, R, G, B, and Alpha. Select the alpha channel only, as if it were a layer. Now you can paint on it with white, black, or grey.
Personally, I find it easiest to make my textures normally, with whatever I want set to white on the alpha separate from any background. Then, once I get everything set up exactly the way I want it, I duplicate the layer bits I want white on my alpha, combine them, lock the transparency, and dump them full of white. Then put a new layer behind it and dump it full of black. CTRL-SHIFT-C to copy combined, and then switch to the alpha channel and paste the result into it.
You do need to have your image flattened before saving as a DDS too, so I tend to work in a new document rather than the same one - that is, paste the alpha into the alpha channel of a new document, set up my textures in one and copy them and paste them into the RGB of a new document... just easier that way, though you can do it all in one - just make sure to save a layer-separated copy first.
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