Since this is a fresh new community, I'm just going to start from the bottom up, with the basics.
1. Cropping & resizing an image to make an icon
First, open up your copy of photoshop and then open up your image. You can drag a picture from your desktop, any file folder, browser, or just go file>>open
Second, grab your select tool, or the Rectangular Marquee tool, and hilight the part of the image you would like to use for an icon. Copy it (hit ctrl and c at the same time on your keyboard OR just go Edit>>Copy)
Third, create a new image. You can go File>>New or hit Ctrl and N on your keyboard.
A window will appear, asking you about your new image's properties. Make sure that the width and the height are equal to each other. Normally they're not, you can just manually type in the new sizes. Also, below that will be the resolution. Make sure it says 72, or it will mess up your text later.
Once you have the new image open, paste the image from your clipboard onto the new image (Ctrl V or Edit>>paste) You should now have a perfectly square version of your image.
Press Ctrl and E. This will flatten your layers.
Next go to Image>>Image Size and resize your image to 100x100. Save your file as either a level 12 jpeg or a png file. Never ever save an icon as a gif unless it animates. Png files preserve quality more than any other file type.