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You will want the most recent, stable, fully released version of Windows NT. Because Microsoft tends to have very long prerelease periods (beta versions of the operating system now called Windows 2000 were in circulation for at least two years before the final release), it becomes tempting to avoid future upgrades by using prerelease operating systems. Don't do it. It isn't going to significantly improve the upgrade situation, and it will mean that you're running critical systems on unsupported software.
In addition to the Windows NT software itself, you will want to get the most recent version of the relevant Resource Kit, which contains useful documentation and tools. These resources are essential for all Windows NT administrators but will be even more reassuring if you come from a Unix background, since they include many command-line oriented tools that will be familiar to Unix people.