Welcome to LQ!
To be honest, there are probably more similarities between the various flavors of Linux than there are differences. For example, the new version you're looking at, CentOS is an almost exact copy of Red Hat Enterprise Linux. Because most of the software is covered by open source licenses (frequently the GPL, but not always), the CentOS group can take the RHEL (which Red Hat charges for) and after stripping out Red Hat logos and copyrighted material, distribute it.
So if you're already familiar with a different distribution of Linux, you'll probably get the hang of CentOS in fairly short order.
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