$hrec{'Comments'} = \@names;
$hrec{'Names'} = \@comments;
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Any reason to switch the keys and values? :-)

Another solution would be to store the pairs "Name / Comment" in a simple hash

... unless the OP really needs to preserve the order. While I don't see the importance, it could be that way it has to, whatever the reason the person who gave the assignment (if it is).

Update

the best solution would be using Text::CSV_XS

I'd say that the core problem is arranging the data structure, not parsing the source file. While using that module might be one of the best among its competitors, it does solve only half the problem.