After loads of digging around I found how to add items to an existing picklist in SalesForce.
Initially, I was clicking on the Edit link next to the picklist, but this didn't have option to add item.
To Add a new item you should click on the picklist name and scroll down to the bottom of the page where you can see the fields to delete, replace and reorder the options.
Book marked, I enjoy your blog! :)