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It's pretty intuitive - you just need to go into Extra -> Preferences, and the first tab you'll see is System Folders. Starting from the top of the list, click a line, click the ... button that appears at the end of the line, and navigate to the folder where that EP is installed. You can also type or copy and paste the folder locations, if that's easier for you.
If you have UC, your installation directory will likely be in C:/Program Files (x86)/Origin Games/The Sims 2 Ultimate Collection, and I'll attach a list of which EPs are where at the bottom of this post. You'll also want to point the Savegame line to the TS2 folder in your Documents (if it's not already correct), and if you want to work with texture images, you'll need to install the DDS Utilities from nVidia and point the Nvidia DDS Tool Folder to wherever you installed them.
Once you've done that it's worth checking that the appropriate lines in the File Table tab don't say "(Missing)" at the beginning unless they are for EPs/games you don't have - you may need to restart
SimPE before doing this.
UC install locations:
Basegame - Double Deluxe/Base
Uni - University Life/EP1
NL - Double Deluxe/EP2
OfB - Best of Business/EP3
Pets - Fun with Pets/EP4
Seasons - Seasons
BV - Bon Voyage
FT - Free Time
AL - Apartment Life
M&G - Fun with Pets/SP9
FFS - Fun with Pets/SP1
GLS - Glamour Life Stuff
Celebration - Double Deluxe/SP4
H&M - Best of Business/SP5
TSS - University Life/SP6
K&B - Best of Business/SP7
IKEA - University Life/SP8
What I lack in decorum, I make up for with an absence of tact.