Not sure if there are any great resources online but there isn’t that much you need to know. I’d say just download it and mess around. Here’s some random tips:
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Windows has its own terminal package manager called winget, it’s very useful.
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Nobody uses CMD anymore, everyone moved onto Powershell. The new windows terminal is also nice.
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Windows has a lot of random features and controls hidden in its registry, which you can access via regedit. You usually don’t want to mess around with it but sometimes it is useful.
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There are a lot of scripts online to de-bloat windows and quickly default to the best privacy settings. I’d run that if you’re setting up a new install. Note that some of it comes back every time you update and you’ll need to run the script again.
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Just understand the file system well and how to use the control panel and firewall and you’ll already be ready to go as a sysadmin
Oh and one last thing, you may want to install PowerToys. It’s an official program that has a suite of features for power users, things like bulk renaming, easier access to environment variables, checking which files are in use by which apps, and a couple of other neat stuff. I use the color picker all the time.