A CPL is most effective when you are at right angles to the suns's rays.
At high noon, a CPL should be effective at just about all compass points since the sun is more or less directly overhead. At sunrise/set, the more the sun is at a right angle to where you're looking then the more effective it should be.
One way to understand where the maximum effect will occur is the "rule of thumb"... literally. Point your index finger at the sun and hold your thumb out at a 90˚ angle from the index finger. Now rotate your wrist keeping the index finger pointing at the sun. The thumb will point in the directions where polarization is most effective.
Hope the above helps..