If by "where appropriate" you mean, "responding to a suspected or confirmed case of COVID-19" then yes. If you mean "wear PPE (for COVID-19)" more generally, then the guidance does not state this.
Here's what it says about PPE (bold bits my emphasis):
PPE protects the user against health or safety risks at work. It can include items such as safety helmets, gloves, eye protection, high-visibility clothing, safety footwear and safety harnesses. It also includes respiratory protective equipment, such as face masks.
Where you are already using PPE in your work activity to protect against non-COVID-19 risks, you should continue to do so.
At the start of this document we described the steps you need to take to manage COVID-19 risk in the workplace. This includes working from home and staying 2m away from each other in the workplace if at all possible. When managing the risk of COVID-19, additional PPE beyond what you usually wear is not beneficial. This is because COVID-19 is a different type of risk to the risks you normally face in a workplace, and needs to be managed through social distancing, hygiene and fixed teams or partnering, not through the use of PPE.
The exception is clinical settings, like a hospital, or a small handful of other roles for which Public Health England advises use of PPE. For example, first responders and immigration enforcement officers. If you are in one of these groups you should refer to the advice at:
https://www.gov.uk/government/publications/coronavirus- covid-19-personal-protective-equipment-ppe-plan/covid-19- personal-protective-equipment-ppe-plan
and
https://www.gov.uk/government/publications/covid-19- decontamination-in-non-healthcare-settings/covid-19- decontamination-in-non-healthcare-settings.
Workplaces should not encourage the precautionary use of extra PPE to protect against COVID-19 outside clinical settings or when responding to a suspected or confirmed case of COVID-19.
Unless you are in a situation where the risk of COVID-19 transmission is very high, your risk assessment should reflect the fact that the role of PPE in providing additional protection is extremely limited. However, if your risk assessment does show that PPE is required, then you must provide this PPE free of charge to workers who need it. Any PPE provided must fit properly .