moony Will validate and test now brb
EDIT: I have been able to verify call waiting to be working fine with my carrier. This suggests a carrier related issue, now without teaching you to suck eggs, can you double check that you have the feature available in your carriers account settings first, ensure then that the stock dialler app is selected as default across all users, and that the setting is enabled, if in a secondary user, ensure that this has telephone/sms granted to it via SETTINGS > SYSTEM > USERS
Then we can go from there. This is definitely not a GrapheneOS related issue as I've been able to confirm call waiting works on the latest release on my Pixel 8.
I appreciate you may not want to but knowing the carrier would help also.