I'm working on a couple plugins but I have a question about incorporating the metadata NameValueCollection. Is there a plan in the future to support duplicate metadata properties with different values; for example, ContentRating=G and ContentRating=PG in the same collection.
If no duplicate key support is planned then it seems that it would be a better idea to change the data type to a generic dictionary. Dictionary This gives you about 3 to 4 times better performance in lookup queries and makes working with Key-Value pairs a little easier for you and us.
Also it seems like the documentation in this area is a little lacking but I can go into that another time.
Content Rating
What values are accepted for ContentRating? I'm assuming the same values that are in the ratings drop-down in the settings GUI.
[G,PG,PG-13,R,NC-17,TV-Y,TV-Y7,TV-G,TV-PG,TV-14,TV-MA]
What is the rating value for "Not Rated" or "Unrated"? Wikipedia says NR.
Rating
What values are accepted for Rating? I'm thinking a 0.1 through 5.0 or maybe just whole numbers 1 - 5.
Sort Index
How is the SortIndex used? Can I use an integer value from a counter? Also, can this number start over at 1 for each folder group or should each folder keep incrementing.

We don't have any plans to allow duplicate metadata properties, so your suggestion to use a generic IDictionary is a good one. We will look into this for a future release of the plugin API.
The acceptable values for ContentRating are exactly what you listed. This is clearly missing from the docs, and we'll add it. We don't specifically parse for "Not Rated" content -- you should just use "NR" for now.
The value for Rating can vary from site to site. It depends on their rating system (some go to 4, some go to 5, etc.). It's only used for display purposes. The guideline is to use whatever value is presented from the source content site.
The idea with Sort Index is to force custom sorting for devices that default to always sorting alphabetically (i.e. the Xbox 360). You can use it both for folders and for items within a folder. There is no need to increment the value across folders. It's only for a single given folder view, and you should prepend 0's as padding as appropriate, to guarantee your own desired sort order.
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