Technical skills can be obtained but they are something that anyone can get.
The soft skills are important too. I have managed Exchange in the past and I'm currently training for my first SQL Server qualification after a year of optimising and improving the maintenance of some business critical databases. (About 10 years of SQL/Access experience from before that)
Both require the ability to maintain uptime, schedule appropriate and timely maintenance and the ability to fall back should your "easy" upgrade go completely wrong. (This is often not your fault!). Have you set up WSUS to roll out Windows Updates to computers for you? Do you vet updates and roll them out to small subset of PCs before allowing the update to go out across the network to make sure that there isn't an issue? One rogue update can cause a day of grief if you have to manually uninstall it.
Do you maintain backups? Do you test them regularly?
Do you produce good, well written documentation? You may be replacing somebody who has been sacked as something has gone wrong and their documentation consists of post-its on servers saying "reboot me every Thursday at 5pm, managers in a meeting then.".
Things like this are probably more encouraging to an employer who has critical services (and all services become critical if they go offline!). Eager people can learn fast, they can also make critical mistakes very quickly if they make quick assumptions.
I have only recently started with the SQL Server books and—to my surprise Microsoft—I have been pleasantly surprised. They acknowledge that they cannot teach a fixed solution. The books teach that "X, Y and Z are solutions", but also ask you know the reasons WHY you would pick one above another in a given situation.
I second the idea of helping a voluntary organisation as well then are often in need of expertise and going into a real world scenario and being able to fix issues and improve systems is valuable experience.