It seems like we've been waiting forever for an official build of VLC to land in the Play Store, and that day has finally come... for some people, anyway. First off, the build that just landed in the Store is for devices with ARMv7 NEON CPUs only. This includes most modern processors, like Tegra 3, Exynos, OMAP4, and Snapdragon S2, S3, and S4. If you have an older processor, like Tegra 2 or one that uses ARMv6 architecture, then a build for your device should be available "in a few days."
While this version is beta, it still supports all the features that users of VLC's desktop software have come to expect, like playback of nearly any video or audio file, media library, support for multi-track audio and subtitles; as well as some mobile-specific goodies like auto-rotation, aspect ratio adjustments, and gestures to control volume.