You have your usual Win32 API functions found in libraries like Kernel32, User32, and GDI32, but since after Windows XP, those don't actually make system calls. The actual system calls are found in NTDLL and Win32U. Lots of functions you can import, and they're basically one instruction long. Just SYSENTER for the native version, or a switch back to 64-bit mode for a WOW64 DLL. The names of the function always begin with Nt, like NtCreateFile. There's a corresponding Kernel mode call that starts with Zw instead, so in Kernel mode you have ZwCreateFile.

But the system call numbers used with SYSENTER are indeed reordered every time there's a major version change to Windows, so you just call into NTDLL or Win32U instead if you want to directly make a system call.