Can I file my wife's return with me even if it is first time for her?

[TurboTaxJennifer]

Yes...and no.

Yes, you can prepare a "coupled" return (both returns prepared simultaneously).

Since it's your wife's first return, she will likely be ineligible to use CRA's NETFILE service. So, rather than sending hers electronically, just print and mail her return. This has no impact on your eligibility to use NETFILE.