Quick steps:
Create all 3 folders in the location you would like them in.
Open Orphalese Folder Options
Select the correct folders using the ... browse button.
Step-by-step to changing the default location:
Access your My Documents folder (Start>My Documents)
Make a new folder called Orphalese
Inside that folder, create three folders:
Packs
Spreads
Readings
You need to copy a deck into this new Packs folder, or it won't allow you to change the default location of the decks. If you open an explorer window you can easily copy from:
C:\Program Files\Orphalese\Orphalese Tarot\Packs to
C:\My Documents\Orphalese\Packs

To open an explorer window: Start>My Computer>Double click on C, and click on the Folders icon at the top. This will open a window where you can have the file you want to copy in the right hand pane, and the folder where you want to copy to in the left hand pane, and just drag and drop the folder.

Open Orphalese
Right-Click on the Deck and select Options or F9

Select Change Setting (for all decks)

Select the Folder Tab

Click on the ... (browse button) for the Decks Folder

Make your way to the location of your My Documents>Orphalese, and select the Packs folder.

Repeat for the Spreads & Readings folder.
Your done!