So much to look at

Is there a LibraryThing walkthrough guide to maybe explain all the ins and outs of this site?

All of them? Not really :)

But the tour will get you started: http://www.librarything.com/tour/ and then the official FAQ page will give you some more pointers: https://wiki.librarything.com/index.php/Help_and_FAQ

After that - just start poking around and ask when you get lost :)

First of all, welcome! And as AnnieMod said, don't hesitate to ask questions. Honestly, LibraryThing's greatest help resource are its many long-time members who are generous with their help and advice.