I'm not feeling so hot so I'm not really inclined to fully test this thought process out.
If Autoplay is disabled on that PC, there's not a whole lot you can do to get around that without doing some partition voodoo to bypass it. So if you can accept a one click operation, in lieu of autoplay, you should be OK. I'll leave it to you to figure out how to get a script to autorun when a drive is plugged in if such operation is allowed on that PC.
Second problem is that you need admin rights to make the changes. That said... Try this basic framework I whipped up.
@ECHO OFF
REM SET THE DESIRED DRIVE LETTER
SET testnudr=U
REM GET THE CURRENT DRIVE LETTER
SET testdr=%~d0
REM PATH TO THE DISKPART SCRIPT FILE
SET testfile=%~d0\test.txt
REM USE DISKPART TO "SET THE FOCUS" TO THE DRIVE
>%testfile% ECHO select volume=%testdr:~0,1%
REM I GET PROBLEMS IF I DON'T HAVE A BLANK LINE BETWEEN EACH COMMAND??
>>%testfile% ECHO=
REM WHY U? MEH.....
>>%testfile% ECHO assign letter=%testnudr%
REM DON'T BLINK, ENTER THE ADMIN PASSWORD WHEN IT COMES UP.
call diskpart.exe /s %testfile%
Open up NOTEPAD (must be notepad or some other "barebones" text editor. Don't use Word for this!!) and give it some random file name. Like
test.bat. Put it into the ROOT directory, eg E:\test.bat of the external drive. DON'T DO THIS ON YOUR PRIMARY INTERNAL DRIVE

Now... copy and paste the code above into that batch file and save it. Now, every time you plug in the drive and it's not the right drive letter, run that batch file.
Some caveats.
I like my scripts to run silent. I didn't capture any errors that might crop up with DISKPART.
The script doesn't bother to check if another drive already exists in the desired "slot". I can add it in easily enough but it would dilute what I wanted to show you, the use of Diskpart.
Diskpart should be on WinXP or later. I tested the above script on Win8 and it worked fine. If you're still using anything pre-WinXp, I can't help you.
You can also accomplish the same thing using PowerShell instead of Batch. I was aiming for lowest common denominator.
Here are some links that are worth reading.
Windows Batch Scripting
http://en.wikibooks.org/wiki/Windows_Batch_ScriptingDiskPart Command-Line options
http://technet.microsoft.com/en-us/library/cc766465%28v=ws.10%29.aspxBe careful with it. Only you can be responsible if you don't read up and understand what each command does.