This was over 10 years ago (i.e. before the days of standardized online applications), but what I did was submit my cover letter and resume via email (pdf), and then followed up with a hardcopy printed on premium weight letter paper in a 9x12" envelope (so it wouldn't be folded). Not sure if it made a difference (as I believe one of the interviewers I met with just had the pdf version printed out) but I wanted to do whatever I could to make my application physically "stand out" from the others.
I should also add, sending both a soft and hard copy version of documents/correspondence is not uncommon in my industry so that is why I thought to try it...
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