As MrEBear says, you'll need to cancel one of the policies, as there's no benefit to having the two in place at the same time.
I'm assuming that both employers pay for the cover as a benefit of employment, and it's not deducted from salary. If so, the two policies are costing you a little more, because you're paying BIK on two policies.
As it's the employers money that is funding these policies, I don't think Quinn will be able to "re-route" some of the money from one employer to fund an upgrade with another employer. You or your wife should talk to your respective employer to see if they'll consider a cash alternative to health insurance, given that it's already being provided by another employer. Or instead of paying for family cover, maybe each of your employers will just pay for one person each at a higher level of cover.
You'll need to talk to them anyway to sort out the cancellation, because Quinn can only accept that from the employer, so see what your employer says. Just bear in mind that they'll want to be seen to treat all employees the same, so they may have some resistence to changing the benefit in individual circumstances.