Looks can be deceiving. It's very easy to use, though it provides a (at first glance) confusing interface, you are only wanting it to do one thing: Tell you what your DLLs or EXEs depend upon. That's just the left-panel in a normal "collapsible tree view"-style widget.
Dependency Walker looks like a tool for hacking binaries and it looks intimidating to use.
And it's not for 'hacking' binaries, just for viewing the binaries. It's not a hex-editor, I don't think. Don't go off of the screenshot on the page I linked - that's what's shown if you "uncollapse" everything to make it viewable - which makes it look more confusing then it really is.
My two greatest problems as a programmer is shying away from what looks confusing without actually investing even an hour to figure it out, and trying to accomplish what seems easy, without taking an hour to plan it through.