The reason there is some overscan is because the PC is expecting the image to stretch all the way to the edge of the tube. This is normal with a regular CRT PC monitor.
However, on this screen there is quite a bit of bezel covering the edges of the screen. If you were to remove the plastic housing of the monitor it's likely you would see a near perfect image.
When you press the underscan button it shrinks the image so that you may check what parts of the image might fall in the overscan area. This is usually very important for video production, which this monitor was originally designed for.
So, how can you remedy this problem?
This monitor has a digital on-screen display and it should have a service menu. Within that menu will be controls to adjust the horizontal and vertical size of the screen.
HOWEVER
The service menu is not to be taken lightly. I suggest you do some serious reading on the subject before embarking on such an endevour. It's not the same as using the h-size and v-size controls on an old pc monitor. There are other factors to consider. Monitors such as these usually have internal digital video processors that expect the screen to be a certain size in order to provide the highest quality of image. They also expect a certain "background" size for the screen image to be displayed on.
My suggestion is to just live with the overscan. I've had it on several of these monitors and once you understand what is going on it doesn't bother you as much any more.
But if you want to go the trouble there should be a control labeled H-pos on the front or back of your monitor. It might be a little hole in the back that you will need to stick a flat jewely screwdriver through to access the knob. You can use that a little bit to make the image fit the screen better.
Additionally, you can also muck around a bit with advancemame, soft 15khz, and groovymame in order to create a custom video signal with an altered front and back porch that will allow your image to fit your monitor more correctly. You will probably have to a bit of trial and error and some research on creating custom video modes to get this to work.