It is likely a challenge for the engineer who has spent their studio life translating a musical performance (or series of musical performances) into a stereo perspective for presentation. Studios and playback systems have been stereo-capable for decades, and surround's only correlation is much more recently in theaters and live venues. We offer these thoughts to aid the mixing engineer, producer, and artist in defining a 'starting point' so that they can move more quickly into the task of 'making music in surround'.
Now for the mixing 'concept'. No matter what you intend to do, or who may be listening to it, there are several rules or practices that have been developed.
Rely on the Left and Right Front speakers to provide the musical 'foundation'. There should be enough information here to tell the musical story, particularly in the bass and vocal region. You may supplement this by adding foundation to the other speakers too.
The Center Front should be used to support the Front Stereo perspective. It is particularly effective at 'nailing down' the primary vocal or lead instrument location. Engineers often put some of the drum kit here (snare and kick, mostly) and a bit of the bass as well. Remember that not all home playback systems will have a properly placed center speaker, and your musical presentation should not rely on this element to be understood.
Surround speakers are where the fun begins! Be creative, but don't overdo the 'pan-around' effects. Most mixers will use these speaker locations to enhance depth and separation. A mix for a 'live video' would seem distracting if too much energy or instrumentation was from behind the listener, whereas one without video might not. Listen to your mix with the Front Left and Right turned off to scrutinize what is going on there, as well as with select combinations of Front and Rear speakers.
Last but certainly not least, what about the LFE? Well, as implied by the abbreviation, this is an 'effects' channel. Therefore, use it this way! In many media presentations (DVD-Video, specifically), it will be band-limited to 120Hz, and an individuals 'subwoofer' and receiver settings may affect how it will be reproduced anyway. So...use with discretion is a good guide. If you need special enhancement in a particular part of a song that 'extra bass' will add, use the LFE. If you want to have signal present throughout the song, add some of the bass instrumentation (including kick if you like). Check to make sure that the LFE signal is not 'missed' if is it missing when played back.
As you begin the mixing process, move around the room to determine if anything 'weird' happens (phasiness), as listeners do not always sit in the center of their listening space. The listener should feel immersed in the performance, but not uncomfortable. This is a very subjective definition, and you will have to judge this for yourself. Certain music styles may allow for more 'aggressive' presentations than others.