If the map was drawn in Paint.NET, you will need some way of programatically knowing where the walls are. I'd recommend setting up a Wall class, which creates each section of wall as a rectangle. (The wall you define yourself can be invisible, if you have a background ready-made). Then, for the actual collision detection, you can use a class called BoundingBox. It's actually made for 3D, but you can use it for 2D just fine by only defining the first two values. It has a nice Intersects() method which determines if one BoundingBox is partially inside another.
As for the actual handling of the collision after that, you would be best off finding some way of moving the pac-man's position outwards from the center of the wall, until his left edge is equal to the wall's right edge, for example.
One thing that helps with collision detection is if you define the origin of your sprite as its center, rather than the upper left (as it is by default). This is somewhere in the draw method of the character.