Create a border
- Create a rectangular selection, the size you want your button to be, with photoshop's rectangular marquee tool
- Right Click on the selection choose stroke and use these settings
This will form a part of the border for the button. Also note that the color I used for my buttons is dark grey (it usually looks better than black). Feel free to experiment the border color
Round the corners
- Select the 1px pencil tool
- Draw the new rounded corners for the image just as I have done in the example
- Erase the square corners
- Fill the image with whatever color you want.
At this point your image should look something like this
Pixel Bevel Effect
Use the 1 px pencil tool to draw highlights. Choose a lighter shade of the color than the rest of the button, and start drawing alongside the top left edges of the button. Tip: Hold down the Shift key to draw straight lines.
Repeat the processes for the dark area exect this time use darker shades of color than the rest of the button and draw along the bottom-right edges of your button. This will give it a beveled look. (this is not the same thing as using the bevel option from Photoshop's layerstyles.)
Once this is done right click on the layer choose layerstyles and then goto Drop Shadow and use settings similar to these Dropshadow Settings which I used.
Final Result
If you want to enhance the buttons with some nifty finishing touches, checkout the popular pixel detailing effects tutorial.