This border effect has hundreds of possible variations. Basically you add three thin borders first (add 1or 2 pixel dark from image, 1 or 2 pixels light from image, 1 or 2 pixels black).
Add a colored border of about 25, then a different color border of 10 or 15. Select the 25 pixel border and run PSP's Reflection Effect Pattern. Click on the dice a few times till you get a pattern that has some cutout or indented sections.
I added a screenshot of the pattern settings I used, but you will want to try lots of settings since your original picture size and style will vary. Use the pick to select the color of the indent, then select your outer border and fill with that color.
Now select the border, which should include the indented sections; fill with another color if desired, Selections Float, 3D effects Cutout (H-0,V-0,Opacity-100 Blur 6).
For this image I filled the border with white first to complement my flowers and the yellow. Crop as needed, then add a 2 pixel dark border to finish.