Shop metafields in Checkout Validation API

Yes you are able to access Shop metafields!

In your shopify.extension.toml file you will specify the name-space and key of the metafield you want to read in your Checkout UI extension.

# Loads metafields on checkout resources, including the cart,
# products, customers, and more. Learn more:
# https://shopify.dev/docs/api/checkout-ui-extensions/unstable/configuration#metafields

[[extensions.metafields]]
 namespace = "my_namespace"
 key = "my_key"

And in your extension you read the AppMetafields, or the useAppMetafields react hook.

If you are using React your extension code could look like this.

import {
  Banner,
  reactExtension,
  useAppMetafields,
  Text,
} from '@shopify/ui-extensions-react/checkout';

export default reactExtension(
  'purchase.checkout.block.render',
  () =>