In my opinion, another very important newbie issue is articulations and MIDI velocities. I know its not exactly about mixing, but I think its relevant to what Hetoreyn is discussing, about how we create music with sample-based orchestral libraries.
There is a profound psycho-acoustic illusion that happens - an instrument may seem like it is being played at a consistent volume and style, but in actual reality there can be surprisingly large differences in volumes and articulations between (and within) each note. This is more than just "humanizing" by introducing randomness. A professional performer has solid control over these subtleties, and often the performer himself/herself doesn't even realize they are varying the volume and attacks of their notes, but they are just being musical.
When hearing newbie compositions, the compositions are often pretty great, but if the articulations sound bad, I think audiences quickly react negatively to it - it is at least as important, if not more, than mixing problems such as loudness or reverb for beginners.
Newbies should not be afraid to take some extra time to try various crazy articulation changes (sometimes even a new articulation per note) and exaggerated dynamic changes that emphasize rhythm or tension in a passage =) With practice, this extra time effort disappears, but the knowledge gained of how "real" and "perceived" volume and articulation changes correspond to each other is a very powerful tool to convey musicality.
Perhaps the best example to illustrate what I'm saying is fast 16th notes. Round robin samples help greatly, but varying MIDI velocities enhances musical phrasing. Its possible to add some "vigorous" feel by accenting the 1st and 3rd 16th notes (out of every 4 notes) just slightly, accenting the 1st slightly more. When doing this, tension can be built by removing the accents just before an important downbeat, instead using a small crescendo in the MIDI velocities. In some cases, it might even be useful to accent the 2nd 16th note immediately after a downbeat, to overcome masking issues or to emphasize the start of a fast passage.
In another example, I found that inserting a sustained note among sforzando notes can sometimes sound like a nice tension build into the next sforzando downbeat. Its not something that might actually be found in the written score, but it still would have sounded that way when the musician played it.
Hetoreyn, about reverb - are you suggesting that non-convolution reverbs available in most DAWs can sound convincing enough? If you are claiming that, I would be interested to know some details about how you use them. Also, you mentioned that your "small setups" often sounded better - can you please elaborate what those setups are? I would like to try some of those techniques if you recommend them. In my (limited) experience, I was unable to get anything to sound authentic, except a "true-stereo" convolution reverb... and even then, comparing it to classical CDs I have, there is a sense of "space" that comes from realistic early reflections which even true-stereo convolution reverbs cannot achieve. I'm on the verge of getting Vienna MIR just to solve this problem... but I'd like to try what you recommend first =)
Cheers, ~Shawn