For simplicity, you can declare just the config you want to overwrite, then mount it onto opt/bitnami/postgresql/conf/conf.d/postgresql.conf.
For example I have this config file
➜ code cat postgresql.conf
log_connections = yes
shared_buffers = 128MB
log_min_messages=DEBUG5
log_min_error_statement=DEBUG
➜ code pwd
/Users/hoaphan/dev/code
➜ code docker run --rm --name postgresql -ePOSTGRESQL_PASSWORD=123456 -v /Users/hoaphan/dev/code/postgresql.conf:/opt/bitnami/postgresql/conf/conf.d/postgresql.conf bitnami/postgresql:15.2.0
You can verify that this is effective when compare the mount of logging:

with just (no config mounted)
docker run --rm --name postgresql -ePOSTGRESQL_PASSWORD=123456 bitnami/postgresql:15.2.0

Not recommended. But if for some reason you still want to override the full original config, you can:
start the original container (eg: docker run --rm -it bitnami/postgresql:15.2.0 bash)
copy the original config out onto your host(here I take the whole directory)
docker cp postgresql:/opt/bitnami/postgresql/conf .
now after edited the conf/postgresql.con, I start another, overriding the full config:
docker run --rm --name postgresql -ePOSTGRESQL_PASSWORD=123456 -v /Users/hoaphan/dev/code/conf/postgresql.conf:/opt/bitnami/postgresql/conf/postgresql.conf bitnami/postgresql:15.2.0
similar result, the config should be effective

Also if you postgres via binami helm chart:
helm repo add bitnami https://charts.bitnami.com/bitnami
helm install myrelease bitnami/postgresql
I'm pretty sure the https://docs.bitnami.com/kubernetes/infrastructure/postgresql/configuration/customize-config-file/ is BS from the look of https://charts.bitnami.com/bitnami/postgresql-12.4.2.tgz
But you can add your config file using a values.yaml with content like:
primary:
extendedConfiguration: |
log_connections=yes
log_min_messages=DEBUG5
log_min_error_statement=DEBUG5
Then
helm install myrelease bitnami/postgresql --values values.yaml
will create ConfigMap like this and mount it into the running container as /opt/bitnami/postgresql/conf/conf.d/override.conf, postgres will know to pick it up and apply.
apiVersion: v1
data:
override.conf: |-
log_connections=yes
log_min_messages=DEBUG5
log_min_error_statement=DEBUG5
kind: ConfigMap
metadata:
annotations:
meta.helm.sh/release-name: myrelease
meta.helm.sh/release-namespace: default
creationTimestamp: "2023-05-03T09:13:58Z"
labels:
app.kubernetes.io/component: primary
app.kubernetes.io/instance: myrelease
app.kubernetes.io/managed-by: Helm
app.kubernetes.io/name: postgresql
helm.sh/chart: postgresql-12.4.2
name: myrelease-postgresql-extended-configuration
namespace: default