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How do I configure the Open Graph plugin?

You don't; there's nothing to configure and there is no admin page. By default, it will use whatever standard WordPress data it can to populate the Open Graph data. There are very simple yet powerful filters you can use to modify or extend the metadata returned by the plugin, described below.

How do I extend the Open Graph plugin?

There are two main ways to provide Open Graph metadata from your plugin or theme. First, you can implement the filter for a specific property. These filters are of the form opengraph_{name} where {name} is the unqualified Open Graph property name. For example, if you have a plugin that defines a custom post type named "movie", you could override the Open Graph 'type' property for those posts using a function like:

function my_og_type( $type ) {
    if ( get_post_type() == "movie" ) {
        $type = "movie";
    }
    return $type;
}
add_filter( 'opengraph_type', 'my_og_type' );

This will work for all of the core Open Graph properties. However, if you want to add a custom property, such as 'fb:admin', then you would need to hook into the opengraph_metadata filter. This filter is passed an associative array, whose keys are the qualified Open Graph property names. For example:

function my_og_metadata( $metadata ) {
    $metadata['fb:admin'] = '12345,67890';
    return $metadata;
}
add_filter( 'opengraph_metadata', 'my_og_metadata' );

Note that you may need to define the RDFa prefix for your properties. Do this using the opengraph_prefixes filter.