I'm so sorry but I have lost my big spoon :bsmilie:
A few pointers: What exactly does this polarizing filter? What exactly is done when the picture style "vivid" is used? Why do you use sunglasses?
read up more on polarizer. Its not just about the vivid blue sky. It cuts reflection. One exampe is it allows you to shoot through glass window. How are you going to achieve that even with photoshop?
Put it simply, polarizers reduces reflections which u cant replicate in Photoshop (depending on the angle of the sun), and saturates the sky a little. Vivid settings just saturate colours, which you can easily replicated in Photoshop.