Look through your viewfinder and rotate the front ring as stated above. Never mind about the sun angle - you will see the changes through your viewfinder. There will be less change if the sun is not in the right position for optimum polarization, but you will choose your shot normally for composition and then get whatever help the polarizer will give you.
With a large hood, it is often difficult to rotate the front ring. I just insert one finger against the knurled ring and rotate that ring. I use a screw in round hood on my 70-200mm f/4L IS lens. The CPL fits on the lens and the hood is screwed into the CPL (if the CPL is not a front thread-less wide angle model). I rotate the CPL by simply rotating the hood. It works great! It doesn't vignette used on a 1.6x camera and it protects the lens from flare and from damage as well as the OEM hood.
A few more uses for a CPL which I did not notice anyone mentioning:
Deepening the color of the sky also reduces the dynamic range of the image to one which can be captured by the sensor - fewer burned out white skies.
The reduction of reflections does wonders for foliage - especially wet or damp foliage. I even used a CPL to great effect in the Hoh Rainforest of Washington State's Olympic Peninsula. The reduction of reflections allowed a better saturation of the color of the (constantly wet) foliage. The 2 stop or so light reduction forced me to use a tripod but, that was a good trade off.
The CPL will also do a great job in capturing saturated colors in rock formations due to elimination/reduction of reflections. This is very evident in pictures of the red colored rock formations in the State of Utah.
CPL will reduce the reflections of water droplets and other particulates in the air and thus reduce the impact of haze and fog on your image.
The CPL is one of the few filters the effects of which cannot normally be duplicated in Photoshop. As an example, in reducing reflections from water and windows, you can see beneath the water and through the windows. You cannot duplicate that in Photoshop because you never had the image of what was under the water or behind the window in the first place.