1. Pick the two images you want to use and open it in Photoshop...
2. Hold down the "Lasso Tool" and select the "Polygonal Lasso Tool" on your tool bar. The "Lasso Tool" is located beneath the "Rectangular Marquee Tool." I love this tool because you can place a marquee around the image you want without haveing to hold down the mouse (which can be a pain). Anyways, the image should look something like THIS with the Marquee around it.
3. Now cut the image from the window with ctrl+x, open a new window making it larger in width than what the image you just cut is and paste it into the new window with ctrl+v. Should look something like THIS. You can move the image around in the window to about where you want it like I did. I moved it over to the side because of the straight line from where Albel was against the side of his original window.
4. Now copy and paste your other image that you're using as the background onto the new window. Just copy and paste the whole thing. At first it will cover up the other image. Just go to your layers and move it below that image to put it behind it. Now it should look like THIS. Move the images around till you find a spot that you think looks nice for your icon.
5. Now, select the "Rectangular Marquee Tool" and hold down the shift key as you select the area you want to use as your icon. Holding down the shift key helps you make a perfect square.
6. Go to "Image" and select "Crop." Then go to "Image" and "Image Size." Change the size to 100x100 with Resolution 72. Go to "Layer" and select "Flatten Image." Now it should look something like this.
Now you have a beautiful base for your icon. ^_^
7. Do you have text in mind for your icon? I hope so =P I've decided to just go with the character's name, Albel.
8. Now make a new layer
9. Take the eyedrop tool and pick a light color from the image that you think would look good as a text color. I picked the color of the sky. (The code for this color is #e9feff) Now write the text where you want it on the image.
10. So you can see the text better, I'm going to show you how to stroke. Eyedrop the color you want to border the lines of the text to make it easier to view and nice to the eyes. I'm useing Albel's skirt, code #534e55. Copy the code cause you'll need it when you stroke the text. Go to Layer, Layer Style, Stroke. Change the color code, set it at two pixel, set it at multiply with an outer glow.
11. Go to Layer, Flatten Image
12. Now, I feel like this image really needs something to bring it out, so we're going to give it a border. I usually use black. Change the color to black and then switch the color tablet to the back color so the black is in back. (All this is on your tool bar). Go to Image >> Canvas Size. And a window should pop up. Make sure you have a check by "Relative" and change the measurements to pixels and the number in both spots to 4. Say okay, and voila! There's your border. ^_^
13. Now go back to Image >>> Image Size. Change the image's size back to 100x100.
13. Save the icon by going to File, Save For Web, make sure it is being saved as a GIF, click save, and name it.
I Hope That This Helps! ^_^ If you have questions feel free to ask =D And I'd love to see what you've made useing my tutorial. *wink*