This is the first tutorial I've written so sorry if it doesn't make sense. I wrote it in PSP 9, that's the program I use. I'm sure if you alter things it can work in other versions of PSP as well.
1. Take the image you want to outline. It has to be a cut out. I'm using this one:
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2. Go to selections>select all. Your image will look like this:
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3. Then go to selections>float. Your image should look like this:
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4. Open up a blank image (file>new) and make it the color you want your outline to be. Make sure you make it bigger than your image. I'm using a white one.
5. Go back to your image and copy it (edit>copy) and then paste it as a new image on your blank color. (edit>paste as new selection).
6. Make sure your image is still selected and looks like this:
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7. Go to selections>modify>expand and you'll see this window pop up:
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8. I usually put it between 2 & 4 pixels. This one is at 3. This is what it will look like:
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9. Now all you have to do is copy it (edit > copy) and paste as a new layer onto the image you want to use it on. This is my result:
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And that's it! It's actually really easy.