im not an expert but basically i just use trial and error.
often it's a matter of one early url leading indirectly to another - so i usually just take the last url pointing to a stream that works.
so an http url will lead to a mms url, and so i take the mms. i *think* a reflector just bounces you to another url, so you would again want the last one. sometimes a recording program like streamboxvcr will like one url and not another, so sometimes it's trial and error.
"simplify url" just removes parameters at the end of a url, like "mms:\\cspan.org\hearing.rm?mode=compact" will change to "mms:\\cspan.org\hearing.rm", which is usually what you want. rarely hurts to leave in the other stuff, but simplifying the url can make things a bit cleaner.