Being my profession, I know that acoustics is usually the last thing people think about when discussing audio, and yet, it is the most important because it has the most impact on the audio experience. Here are a few basic things to consider:
There is a hierarchy to playback systems:
1. Physical set up
2. Calibration
3. Acoustics
4. Equipment
Achieving optimal room acoustics is a matter of controlling noise and vibrations, room modes, first order reflections and reverberation times in a linear fashion.
Regarding your set up, like your speakers, it is beneficial to locate the listener away from the wall to avoid reflections and modes. Without understanding your specific room characteristics, I will just generalize that for a typical (not too live, not too dead) residential room it's a good idea to address the low frequencies (room modes) first, then the first order reflections for each speaker at all six locations, then address the remaining reverberation times.
Regarding interior acoustic treatments, there are three tools; absorption, reflection and diffusion. The common room treatments, especially the DIY kind, deal only with absorption, and only address about 500 Hz. (essentially Middle A on a piano) and up. This approach typically leaves the room sounding too dead in the mids and highs, and slow and muddy below. Knowing how much, of what, where, is one of the ways acoustical engineers can turn the audio experience from ho-hum into WOW!