The "main basic" changes are that .NET's library is object-oriented. For example, instead of global string functions that are spread between System, SysUtils, StringUtils, etc., they're all just static methods on the String class. Instead of global path-manipulation functions, they're static methods on the Path class or the File class. Instead of TextFile/AssignFile/Rewrite, you create a StreamReader (or just call the static File.ReadAllLines or ReadAllText if the file is small). Most things are fairly discoverable with a bit of poking around. There are a few things missing; for example, there's no IncludeTrailingPathDelimiter method in .NET (though you usually don't need it -- Path.Combine is better).
I'll second the suggestion to skip WinForms. If you've used the Delphi VCL, WinForms will be familiar and yet frustratingly, maddeningly inadequate. They took the basic ideas from the VCL but never bothered to give it the slightest depth, or even usability. There's no equivalent for TAction/TActionList, the Dock property (equivalent to Delphi's Align) likes to hide controls behind each other until you mess around with "Bring to Front" / "Send to Back", tooltips require an extra component on your form, there's only a tiny handful of controls, and that's just off the top of my head. Take the time to learn WPF; it's got all the richness of the VCL and more, and will have you spend much less time beating your head against the wall.
The IDE takes some getting used to, but I like it far better than Delphi. You have to learn a different set of keystrokes, but that's no big deal. The IDE is more responsive (none of that locking up during "background" compilation). It also has some kick-ass add-ons -- after you've used ReSharper for a while, you won't miss the Delphi IDE a bit.