In terms of the SFF files themselves (as far as I know) there is no difference at all. There is nothing in the file format or the Roche XML meta data block that I have seen to tell you if the data is single reads or paired ends.
It is all down to the sample preparation. The Roche 454 website has a nice summary of how this works:
If you know you have a paired end SFF file, you should be able to find the linker sequences in the reads - see:
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