There's no major developer-type experience required. Just point the program at the index page for your site, it tries to access all the necessary resources (and warns you of any problems), and at a minimum you're able to build the finished EXE in a couple of clicks.
This isn't really a "compiler" - just a runtime engine which stores your site's resources along with its own files - but it looks much the same to the end user. You're left with a single executable, with no major dependencies, which doesn't unpack your website in order to run, and just displays the web page in a regular Windows frame.
There are plenty of ways to customise the finished application, too (Edit > Project Options). You're able to set the application title, icon, window size, style, border (sizeable or not), set it "always on top", and more.
Please note, while you can use the trial version for as long as you like, it has one nag screen on load, and regularly displays another when a "compiled" application is running.
HTML Compiler worked well for us, converting several CSS games into EXEs which all ran correctly. It's using Internet Explorer's engine to render the pages, though, so might not always deliver the results you expect. The price - $49.95 for a personal license, $99.95 for commercial use - also seems high.