You can not do this natively in windows. The border color and title bar color are tied together under the accent color.You would have to use a third party tool. https://www.stardock.com/products/windowblinds/
or you could install cute-borders which is based on windows-api....that'll make it look even more pronounced borders....I personally use tacky-borders for thicker borders.
Internal: Raid Config 1TB (Samsung MZVL2_512 + Micron 3400_512) NVME SSD
Portables: WD Elements 4tb, WD Elements SE 2TB, Seagate 3.5inch HDD 1TB, WD Blue 3.5inch 512gb, Hitachi 2.5 inch HDD 512gb
Keyboard
Redragon Kitava - Red Switches
Mouse
Meetion GM80 Transformers
Internet Speed
250mbps
Browser
Waterfox (Windows), Kiwi (Android)
Antivirus
MalwareBytes
Other Info
Speaker: Mingo 5.1 Home Theatre System (used everyday since Early 2000 without repair)
Headphone: Ugreen HiTune Max 5C
Earphone: Mi In-Ear Headphones Pro HD Dual Driver (Neutral sound profile)