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Audino and Volbeat both use Substitute, and assuming both Substitutes aren't broken, we move on to the next turn. Audino must have Max EVs in Speed, but Volbeat must not. Audino will then use Simple Beam on Volbeat and Volbeat will use Tail Glow after that. BAM! Maxed out Special Attack. Is there any way to make this better?

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For starters, Illumise cannot learn Tail Glow so your strategy just went down the drain
Secondly, the assumption in which Substitute does not break is a kinda low chance one, due to the low bulk on both of them, especially when pitted against powerful attackers in doubles
Thirdly I'm pretty sure Simple Beam is blocked by Substitute. Just gave a quick trial run on PS, (I decided to use Volbeat), and it's Special Attack still went up by 3 stages.

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Oh I meant Volbeat xD
Only reason to use volbeat - good support set + prankster
In order for Audino to 'outspeed' you have to get rid of prankster.
Might as well use Azumarill without Huge Power while you're at it too.
And sub still blocks i think :P