Quick note: If this is below your level, I apologize. I don't know where you're at, so-to-speak.
If you're nervous about transferring your O/S and data... don't. The reasons for transferring are:
1) better performance. If you're happy on a P4, you probably aren't super-concerned about it.
2) reliability concerns. If this is an issue, consider getting a backup utility so that you can migrate the complete image over to your SATA drive.
But if there's no reason to move your O/S off of your 80 GB drive, then just leave it where it is. Move your data over (in particular, check your "My Documents" folder under c:\documents and settings\) to the new drive, and there you go.
Things to look out for:
1) You'll need to make sure that the motherboard and O/S think the new drive is just an IDE drive; or, you'll need to install device drivers for it. I'm guessing you don't want to mess around with device drivers, so when your computer boots go into the Setup (Fn-F2, or just F2, I think) and check whether there's anything about SATA mode, IDE vs. SATA, RAID, or AHCI. If one of the options is IDE, set it to that.
2) you may be able to use the IDE power connector you already have on the SATA drive. Some SATA drives have both connector types, some don't. My WDs have both.
3) Make sure you're running XP with SP2. With just XP, you may find that the O/S will only "see" 139 GB on your new drive.
A couple of other things you can do to make your system run faster once the new drive is on it:
1) move your pagefile (pagefile.sys) over to the new drive. To do this, you have to set the virtual memory pagefile size to 0 (do this by right-clicking My Computer, select properties. The settings in there), and then set it to be a reasonable size, but now on your D (or E, whichever it ends up being) drive, instead of your C drive. You'll have to reboot in the middle.
2) move your temp directory over to your new drive. To do this, make a new directory on your new drive (e.g. D:\TEMP). Then go to environment variables and point the TEMP and TMP environment variables at the new folder. There are both system- and user-level parameters for these, so don't forget to migrate both.
You'll have some reconfig work getting all of your programs to look at the new drive instead of the old... but the performance benefits will be worth it. Good luck!