Hi Aussie 11
First of all welcome to BE and the India and Goa forums.
Quite a few folks have got PIO cards - quite a few are on the Goa forum so it may be worth posting your question on there too - so I am sure they will be able to advice on documents etc.
Bipat has given you a link to the VFS which is the visa outsourcing agency employed by the Indian High Commissions to deal with all things visa - somewhere on that website you will be able to find a section on PIO applications, which should list the documents you need to produce.
As for how long it takes - well that my friend is the ever burning question that has no definitive answer - this after all is India !!!
- In other words some have got a PIO in 3 months, for others it has been a rather longer wait.....
All the very best with your application
Dread - x