The IP blocking allowed the program to start correctly but according to my client they had other problems using the software and decided not to pursue the issue any further.
Here's what I did for the startup fix.
Block IPs to allow PhotoShow to run without hang at startup.
PhotoShow Express tries to connect to these Amazon's SE servers:
IPSEC configuration Manual Method that blocks specified IPs (Standalone PC):
1. In XP PRO click Start->run SECPOL.MSC (now continue at step 2)
In XP Home click Start->run MMC
Select "IP Security Policy Management"
Select "Local computer" and click Finish
2. Left click "IP Security Policies on Local Computer" on the left window to select it then right click it and select "Create IP Security Policy...".
3. Click Next on the wizard's first page, enter "Block IPs Photoshow Fix" as the Name, and click Next.
4. Clear the "Activate the default response rule" check box, then click Next.
5. Leave "Edit properties" checked and click Finish.
6. Click Add on the Rules tab, then click Next on the first three pages.
7. Under Authentication Method select "Use this string to protect the key exchange (preshared key):" enter any text you want then click Next.
8. On the IP filter Lists: Click Add.
9. For Name: type "Blocked IP List" then Add.
10. Click Next on the first page.
11. Leave Source address: "My IP Address" then Next.
12. For Destination address: select "A specific IP Address" and enter 126.96.36.199 then Next.
13. Leave Select a protocol type: "Any" then Next and Finish.
14. Click Add again following steps 10 through 13 for 188.8.131.52.
15. Now OK out of the IP Filter List dialogue box.
16. Under IP filter lists: select the "Blocked IP List" you just created then click Next.
17. For Filter Action click Add then Next.
18. Enter "Block" for the action's name and click Next.
19. Select Block for the filter action behavior, then click Next, Finish.
20. On the Create Security Rule wizard, select Block, then click Next.
21. Clear the "Edit properties" check box, then click Finish.
22. On the "Block IPs Photoshow Fix" Properties window click Close.
23. Now right click "Block IPs Photoshow Fix" policy and click Assign.
Your policy now contains one rule that blocks the specific IP addresses.