Without any sort of custom headers, the only way to be absolutely sure the file is encrypted is to attempt to decrypt it.
If you attempt to compress the file and it gets smaller, then it is extremely unlikely to be encrypted. If there is a non-uniform distribution of byte values (including plain text!), then it is unlikely to be encrypted.
Those heuristics depend on proper execution of the encryption. If AES is applied to a file one block at time, then patters can emerge in the result, but since you are using CryptoStream this shouldn't be a problem.
If your own code will always be used to encrypt and decrypt the files, then you should consider adding a custom header that indicates it is an encrypted file.
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