Upscaling doesn't look near as good as native 1080p.
Well, for most movies. Some movie's (like Bram Stroker's Dracula), the Blu-Ray transfer is absolutely horrible, and looks like no better than the DVD version.
But yeah, for most movies, especially any titles released in the past 5 or so years, the Blu-Ray version looks much better than the DVD version upscaled.
As far as upgrading your collection, it's not worth it. I'd say only upgrade the movies that you REALLY love, particularly those that would benefit from a clearer picture (the only movies I'll probably re-buy from this point onward is the Lord of the Rings trilogy - my gosh it will look spectacular).
As for new movies, definitely get them on Blu-Ray.