Using Little Snitch to temporarily block all but a few apps

Here's what I'm looking to do: Create a little snitch set of rules or profile that I can enable, and would do the following:

* Block all connections, except
* Apps I choose, such as a Trello Fluid app, chrome, and skype

Is this possible. I notice profiles in the documentation, but I cannot seem to find them in the menu of the app itself. I'm sure I'm missing something very obvious. Any help would be appreciated. Thanks!