Accessing picasa isn't very well explained in the samsung's emanual. When you try to access picasa for the first time in Samsung smart TV you get message saying "Please sign in, use settings to update link site using picasaweb.google.com" or something similar.
So you would be wondering where the heck is settings ? In picasa or in Samsung account ? I know its one of the most unhelpful message from picasa app.
So to access picasa follow these steps -
1. Create a samsung account , Press Smart hub button and then go to Samsung apps , then press Red "A" button for login, Sign in or register for a new Account.
Check your email and activate the account if you are creating for first time.
2. Now Press Smart Hub button again , then press "Menu" button on your remote , select Smart Features from the menu and then select 'link to site' from the right side.
3. Click on Picasa , it will ask for service id and password , if you are using google , this id and password is same as your gmail id.
Once this gets through you should be able to access picasa.