The problem that you will run into is as old as computers. Two people saying "Hello" will make two bit-wise different files and making a computer understand this is extremely tricky.
Microsoft has some libraries that may help. However, they are not a part of the .Net framework and I am not sure how they are licensed. They come as part of the Office Speech Recognition Package.
Giving a percentage of the similarity of two files in general is very easy. Load both files as byte arrays, cycling through, comparing one to the other. Note the number of array items that are equal and divide that by the total number of bytes (use the file with the least number of bytes for this calculation). As stated before however, it won't be a movie-like, "98% Match, this is our guy." Hollywood is still keeping that code a secret. :)
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