There's no real debian liveCD but there are debian based liveCDs like knoppix, mepis and ubuntu.
This is about what you can expect.
http://www.osnews.com/story.php?news_id=2016
It's for debian woody but that's quite old and the sarge installer is supposed to be a bit more friendly. Debian is more advanced because it gives you more options. I found you can give some input that you want a lot of programs installed but I always install no packages and use apt.
Debian might be a bit less good on the automatic hardware detection. Some things you have to do yourself as far as I know.
The installer is not pretty but I didn't found it really hard either. Be sure you know about your partitions before you start though.
A real advantage to more newbie friendly distros is that debian is apt. It's a tool that solves dependencies and makes installing programs really easy.
If you want to invest some time to learn your way around it can be really great, but well to each his own so it might or might not fit you. Only thing you can do is try it out.
Knoppix allows you to install on the harddisk and is a debian install. Other liveCDs can install on the hard disk iirc as well but those have their own package servers which I gather from posts around here are not really good yet as in errors and missing packages because the distro doesn't have a package yet.
