You need bass traps for subwoofer. Those usually go in the corners of the room, where two surfaces meet each other. Check some threads here and at google to find more info.
for main speakers, if you want to treat, there is a simle mirror test to determine the reflection points. Have a friend sit in the listening position, and then you, holding a small mirror in hand (flat, facing the room). Start from the back of the room on the left side of the wall. Start walking slowly towards the front of the room. At some point, your friend will see the reflection of right speaker in the mirror. Mark that position. You would want to put an absorber here. That will take care of the reflection of the right speaker on the left wall. Keep walking slowly towards the front and next your friend will see is the reflection of center speaker. We will talk about this later. Keep going and your friend will the reflection of left speaker. Now, you have two choices here - You can put absorber, but it will make the room quite dead. Instead, if you put diffuser here, it will diffuse the sound and a straight reflection will not occur coming from there and won't interfere as much coming from the left speaker.
Repeat the above with the right wall. This way, you will have taken care of the left and right speaker reflections and made sure that right speaker sound is coming from right only and vice-a-versa.
About center speaker - whether to treat with absorber or diffuser is your choice. You can even leave it alone because, if the center is exactly in the center, then the reflections from left and right will be same and pretty much cancel each other. If the room is not square and you don't like the sound, then measure and decide.
The above will get you pretty much covered from the audio wise. You can offcourse, get the measuring tool out and measure the room response to do more tweaks.