Experience troubleshooting will also be of great assistance when it comes time to start designing systems and networks: you'll know about possible pitfalls and how to avoid them.
In particular I'd say to learn the differences between accessing a host by FQDN or by IP address. That access is to include both ping and net view/use.
I've seen too many sys and net "admins" spend hours tracing cables, reviewing routing and CAM tables, when the problem came down to an issue with naming services (name service unreachable, incorrect addresses configured,...).
Also, when troubleshooting you should be working with many different groups (DBAs, application admin, telcos, desktop support, etc). This expands your understanding and thus your skillset. And gets you closer to the front of the line when an opening is available in one of those other areas.
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