If you're looking at network administration, start looking at diving heavily into the Cisco Certified Network Associate (CCNA) certification, if you can work your way up the chain of that certification you become incredibly employable. You can look at Network+ by CompTia as a foothold or introduction, but CCNA, CCNP and CCIE certs is where the money is.
There is also the Juniper Networking cert, network security, etc... If your spouse has a degree already, I'd start focusing on industry supported certificates.
For Networking: Cisco Certified Network Associate to start. Then look at some other technologies like F5 Local Traffic Manager, Cisco Nexus equipment, JNCIA (Juniper)
For Server/DataCenter/Desktop Virtualization: Vmware Certified Professional (VCP5 currently) - then look at the VCAP.
For Windows Server Administration: the Microsoft Certified Technology Specialist (MCTS) or Microsoft Certified Systems Engineer (MCSE)
Security - Security+, Certified Ethical Hacker (CEH), CISSP, CAP, SSCP. (CISSP is the big one)
Linux - Red Hat Certified System Administrator (RHCSA)
If I get some more information as to her interests, I can provide some good starting material. Some tests require you take a vendor's training class first. Does her employer provide any training credits or budget?
[added] - For the 'focus' degrees, I haven't seen many yet that are still relevant by the time a student graduates. I run an internship program for students where I work and most of them are Juniors/Seniors with pretty worthless knowledge to work as a SysAdmin.
If you want to be employable at 60-120K/yr in any town in America get this solid trifecta: VCP5, CCNA and RHCSA (In that order).
If you want to make 80-150K in all major cities, go the next step up with the VCAP and CCNP.