All right! Here goes...I haven't used PSP in something like four years, so it took me a while to figure this out again. Hope this helps!
(For educational purposes, I am using a larger image than 100x100 so that it's easier to see. Feel free to click on the thumbnails of the screen shots if you need larger images.)
01. Open up your image and crop your base to the desired size.
03. Create a new Vector layer. You may want to reduce the opacity for this layer now. As you work, your image will be obscured by the shape you're drawing, so it's helpful to take the layer down. I tend to use anywhere from 30-60% opacity while I'm working with this tool.
04. Select the pen tool.
05. Configure your settings for the pen tool as follows:**
# New: Shape (make sure the "Shape" button is depressed) Also make sure that the check boxes for Contiguous, Simple Mode, and Create as Vector are checked here!
# Mode: Make sure that the pencil icon is depressed. This will ensure that you are drawing a new vector shape, instead of trying to edit an existing shape.
# Segment type: Be sure the middle icon (Point-to-Point) is depressed. If you have a steady hand, you might be able to do this with the last icon (the freehand button), but I don't so I'm doing this point-to-point. Plus, I find it easier. ;)
# Line Style/Width: Should you decide you want a border around your shape, you can change these settings here. I haven't, but I'm doing it with a solid line and with my width at 1.00 pt, just so you can see what I'm doing.
**A screen shot is provided to help you locate these tools and settings HERE.
06. Now, take your pen tool and begin by clicking anywhere around your subject. (Shown below.)
A.Once you have made your curve, RIGHT-CLICK on the end point of your curve. This will bring up a few options. Go NODE TYPE >> CUSP.
B. Then, take the end of the arms with the arrow, which you created as you made your curve, and turn it in the direction of your next move, otherwise your shape will take all kinds of funny jaunts off in directions you don't want it to go. Now you can continue to draw your path around your subject.
09. All right...once you've made it back around and are ready to close your path, make an anchor point next to the point you started out with. Then, right click that point and go EDIT >> CLOSE. This will close your new shape! YAY!
11. Right click one of your vector layers and go: CONVERT TO RASTER LAYER.
12. Take your MAGIC WAND TOOL and select everything inside of your rasterized shape. THEN, move down a layer to the one with your actual image. Hit CTRL + C to copy everything within your selection.