In my opinion, for learning-purposes I would recommend first getting some exposure/experience with SQL Server 2000. Why do I say this? Because like most commercial software products, each new version is an enhancement to the older/pre-existing version. For example, in the replication sub-system, SQL Server 2005 includes several updates to the system over SQL Server 2000's, but you wont be able to appreciate those updates if you just learned 2005's first nor would their importance be emphasized to you. Just my 2 cents :)
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