HI-FI NEWBIE NEEDS HELP!

OP:

 So if that happens I don’t want to realize that I purchased the lesser quality product even though there was a better quality product for the same price point.

This is where it gets very tricky, because it is quite subjective. Depends on you. 

   I envy you your love for, and expertise in, playing pool.  Many years ago I often earned myself a few beers when playing in the local bars of my college town.  :)  However, I want to point out that your analogies are not exactly parallel.  When playing pool, even though your technique and strategies might be varied, your goal is quite straightforward.  You need to sink the balls you've called into their pockets.  Quite objective.  However, when assembling an audio system, your goal (as David pointed out) is very subjective.  For example, I tend to listen to a lot of acoustic roots music (blues, folk, bluegrass) and I like a relatively "forward" and intimate sound while maintaining a nice amount of "air" around images.  Many of my classical music loving audiophile friends like a much more "removed" sense, as though they're somewhat well back in a symphony hall with good acoustics. So, my perfect sound is quite a bit different than theirs.  Find your own sound and move toward it....
    As far as actually hearing a difference in sound between components, you will unless you have some kinda substantial physical hearing loss.  Many a time an acquaintance of mine has sat in my listening room for the first time saying that they really don't have "good" ears and that they probably won't hear much difference from their car radio, etc.  Within a few tunes, their eyes have widened and they are expressing the various aspects of sound that they've never heard before sitting at home or in their cars.  It's not a particularly special skill.  It's just something to enjoy!
   

Let me put this analytically. I would like to enjoy a system that, at the highest volume I normally listen, gives the clearest music possible.
 

If you mean uber resolution and analytical sound at high volumes, then pro-audio / pro-audio leaning gear. PMC Active monitors, for example, driven by pro gear.

   Just a caution if what you are seeking is "uber resolution".  Although you might "hear" everything, you may not find this kind of system musically or emotionally satisfying over the long haul.  I've encountered systems like this that are very much on the "sterile" side and fatiguing to listen to over time.  Listen for a sound that draws you into the music and provides the "goosebump" effect, even if it's not the most highly resolving system.
   Also, an FYI that the Maggies do tend to sound better with a bit of volume.   Their sound doesn't really "bloom" at lower listening levels.  You also have to be VERY careful with speaker placement.  Inches can make a huge difference, and the listening position for them is quite narrow. My audio room has just one chair.  Something that my wife has commented on more than once...  ;-)  However, it's a great chair to be in late at night, lights down, hoppy craft brew in hand, and a favorite artist hovering in space in front of me.